CN106796378A

CN106796378A - For the counterelectrode of electrochromic device

Info

Publication number: CN106796378A
Application number: CN201580053092.2A
Authority: CN
Inventors: 丹恩·吉拉斯皮耶; 安舒·A·普拉丹; 斯里达尔·K·凯拉萨姆
Original assignee: Soladigm Inc
Current assignee: View Inc
Priority date: 2014-09-05
Filing date: 2015-09-01
Publication date: 2017-05-31
Anticipated expiration: 2035-09-01
Also published as: WO2016036707A2; US20190107763A1; US10684523B2; CN106796378B; EP3677962B1; EP3677962A1; WO2016036707A3; US20220350217A1; US10345671B2; EP3982195A1; EP3189373A4; CN112327556A; US20170255076A1; EP3189373A2; US11422426B2; EP3189373B1; US20200278588A1

Abstract

Embodiment herein is related to electrochromism lamination, electrochromic device and the method and apparatus for preparing such lamination and device.In various embodiments, the anodic coloration layer in electrochromism lamination or device is fabricated to including nickel tungsten tin-oxide (NiWSnO).This kind of material is particularly advantageous, because it is very transparent under its clear state.

Description

For the counterelectrode of electrochromic device

Cross-Reference to Related Applications

Submitted to and entitled " COUNTER ELECTRODE FOR within 5th this application claims September in 2014 The rights and interests of the priority of the U.S. Provisional Patent Application No. 62/046,864 of ELECTROCHROMIC DEVICES ", this is interim specially Profit is applied in entirety by reference and is incorporated herein for all purposes.

Background

Electrochromism be material when different electronic state (usually because experienced voltage change) are placed in optics The phenomenon of the change of reversible electrochemistry mediation is shown in characteristic.Optical characteristics be usually color, transmissivity, absorbance and One or more of reflectivity.Electrochromic material (such as) known to a kind of is tungsten oxide (WO₃).Tungsten oxide is by electricity Electronation and there is the cathode electrochromic material of the coloring transformation that can pass through blue.

Electrochromic material can be incorporated into (such as) window and mirror.Can be by inducing change in electrochromic material And change color, transmissivity, absorbance and/or the reflectivity of such window and mirror.One applications well known of electrochromic material (for example) it is rearview mirror in some vehicles.In these electrochromic rearviews, the reflectivity change of mirror is caused at night The headlight of other vehicles does not upset driver.

Although electrochromism was found in the sixties in 20th century, electrochromic device ran into various asking in history Topic, these problems hinder the technology to realize its whole business potential.

General introduction

Embodiment herein is related to electrochromic material, electrochromism lamination, electrochromic device and for making The method and apparatus for making such material, lamination and device.In various embodiments, counterelectrode material includes the novelty of material Composition.For example, counterelectrode material may include nickel, tungsten, tin and oxygen；It is combined into mixed oxide.Mixed oxide is also May include lithium or other electric charge carriers.These elements are provided and are expressed as " NiWSnO " together.In some feelings Under condition, the composition of counterelectrode material meets some conditions.Exemplary condition may include about 1:1 and 4:Ni between 1:(W+ Sn) atomic ratio, such as in certain embodiments about 1:1 and 3:Between 1, or about 1.5:1 and 3:Between 1, or about 1.5:1 and 2.5:Between 1, or about 2:1 and 2.5:Between 1.Similarly, in some embodiments, Ni:(W+Sn) atomic ratio About 2:1 and 3:Between 1.Another exemplary condition is related to the W in counterelectrode material:Sn atomic ratios.W:Sn atomic ratios can fall About 1:9 and 9:Between 1, such as in some embodiments about 1:1 and 3:Between 1, or about 1.5:1 and 2.5:Between 1, or About 1.5:1 and 2:Between 1.Another exemplary condition is related to the Ni in counterelectrode material:W atomic ratios.In some embodiments In, the Ni in counterelectrode material:W atomic ratios are about 1:1 and 4:Between 1, such as about 1.5:1 and 3:Between 1, or about 2:1 With 3:Between 1.Counterelectrode material can meet one or more of these exemplary conditions.

In in terms of some of disclosed embodiment, electrochromic material is prepared using NiWSnO counterelectrodes material Lamination.NiWSnO materials can meet any one of condition listed above or elsewhere herein or various.Lamination can be wrapped NiWSnO layers is included as anodic coloration material, and cathodic coloration material layer.One example of cathodic coloration material is tungsten oxide. In certain embodiments, ionic conductivity electrical insulating material layer is provided between NiWSnO layers and cathodic coloration material layer. In other cases, NiWSnO is deposited with cathodic coloration material direct physical contact, and is not provided between, the layers single Ionic conductivity electrical insulating material.The lamination can be used when electrochromic device is made.

In a related fields of disclosed embodiment, there is provided a kind of method for making electrochromism lamination.Institute The method of stating may include to be formed the cathodic coloration layer including cathodic coloration electrochromic material and be formed includes nickel-tungsten-tin-oxidation The anodic coloration layer of thing (NiWSnO).NiWSnO can meet above or any one of condition described elsewhere herein or many Kind.Methods described may include and anodic coloration layer direct physical contact deposition cathodic coloration material layer.In other embodiments, The depositing ions conductor layer between anodic coloration layer and cathodic coloration layer.Forming anodic coloration layer may include to splash one or more Shoot at the target and sputtered to form NiWSnO.Sputtering target may include the alloy of metal element and/or metal, this metalloid include nickel, Tungsten and tin.Metal during one or more of targets can be provided in the form of oxide.

In the another aspect of disclosed embodiment, there is provided a kind of electrochromism with NiWSnO anodic colorations layer Device.NiWSnO anodic colorations layer can be met above one or more of with condition described elsewhere herein.Electrochromism Device may include electrochromism lamination as described above.For example, electrochromic device can remove NiWSnO anodic colorations Also include cathodic coloration material layer outside layer.NiWSnO can be deposited by approach described herein.In some embodiments In, anodic coloration layer is substantially unbodied.In some cases, anodic coloration layer includes the amorphous base of the first material Matter, it has the second crystalline material being dispersed in the whole [amorphous.

In the another aspect of disclosed embodiment, there is provided a kind of integration for making electrochromism lamination is deposited System.The system may include：Multiple deposition stations, the multiple deposition station continuously aligns and interconnects and operable that will serve as a contrast Bottom is sent to next station from a station, without making the substrate be externally exposed environment, wherein the multiple deposition station bag (i) first deposition station is included, first deposition station has one or more material sources for depositing cathodic coloration layer；(ii) Two deposition stations, second deposition station includes including for depositing the anodic coloration layer of nickel-tungsten-tin-oxide (NiWSnO) One or more material sources；And controller, the controller has to be used to deposit (i) cathodic coloration layer over the substrate (ii) anodic coloration layer to form lamination in the way of the substrate is transported through the programmed instruction at the multiple station, it is described folded Layer includes at least cathodic coloration layer and anodic coloration layer.

Second deposition station can be configured to deposit NiWSnO to meet appointing above or in condition described elsewhere herein One.In some cases, include one or more for depositing at least one of one or more material sources of NiWSnO Selected from the metal element of the group for consisting of：Nickel, tungsten and tin.In these or other cases, for depositing NiWSnO At least one of one or more material sources include alloy, the alloy include two or more be selected from by nickel, tungsten with And the metal of the group of tin composition.In these or other cases, at least one of sputtering target may include oxide.Various Can be sputtered in oxygen-containing atmosphere in embodiment.

To be more particularly described hereinafter referring to correlative type embodiment herein these and other features and Advantage.

Brief description of drawingsfig

When combine schema consider when can more fully understand it is described in detail below, in the drawings：

The schematic cross-section of some embodiment electrochromic devices according to Fig. 1.

Fig. 2 illustrates the cross-sectional view of the electrochromic device according to the multistep process description provided with regard to Fig. 4.

Fig. 3 illustrates the top view of electrochromic device, shows the position of the groove in cut-in device.

Fig. 4 illustrates the technological process that description makes the method for electrochromic.

Fig. 5-7 illustrates the method for making electrochromism lamination, some embodiments according to the electrochromism lamination Electrochromic device a part.

Fig. 8 A illustrate the integration depositing system according to some embodiments.

Fig. 8 B integration depositing systems with perspective view shows.

Fig. 8 C illustrate modulation conformity depositing system.

Fig. 8 D are illustrated with two integration depositing systems of lithium deposition station.

Fig. 8 E are illustrated with an integration depositing system for lithium deposition station.

Fig. 9 A illustrate the rotary sputtering target according to some embodiments.

Fig. 9 B are shown according to two rotary sputtering targets of some embodiments deposition materials on substrate from top to bottom View.

Figure 10 A-10C are related to material wherein is deposited into the embodiment to main sputtering target using auxiliary sputtering target, according to certain A little embodiments, are then deposited on substrate.

Figure 11 illustrates the hysteresis curve for depositing various optical switchable materials.

Describe in detail

Electrochromic device

The schematic cross-section of the electrochromic device 100 according to some embodiments is shown in Fig. 1.Electrochromism is filled Put and passed including substrate 102, conductive layer (CL) 104, electrochromic layer (EC) 106 (also sometimes referred to as cathodic coloration layer), ion Conducting shell (IC) 108, counter electrode layer (CE) 110 (also sometimes referred to as anodic coloration layer) and conductive layer (CL) 114.Element 104, 106th, 108,110 and 114 it is referred to as electrochromism lamination 120.The operable electricity for applying current potential with across electrochromism lamination 120 Potential source 116 realizes transformation of the electrochromic device from (such as) clear state to colored state.In other embodiments, relatively In substrate by the layer out of order.In other words, the layer is in the following order：Substrate, conductive layer, counter electrode layer, from Sub- conducting shell, electrochromic material layer, conductive layer.In some embodiments, as further discussed below, deionization biography can be saved Conducting shell.

It will be appreciated that mentioning being changed into nonrestrictive and only showing attainable between clear state and colored state An example in many examples of electrochromism transformation.Unless otherwise indicated herein, as long as otherwise mentioning clear to colored Transformation, corresponding device or method cover other optical state transitions, such as non-reflective-reflection, transparent-opaque etc..Separately Outward, term " clear " and " bleaching " refers to optics neutral state, such as not colored, transparent or semitransparent.Additionally, unless herein In it is otherwise indicated, otherwise electrochromism transformation " color " or " color " be not limited to any specific wavelength or wave-length coverage.Such as It will be understood by the skilled person that the selection of appropriate electrochromic material and counterelectrode material determines related possible optical transitions.

In various embodiments herein, counterelectrode is fabricated to including nickel, tungsten, tin and oxygen.In such anti-electricity In the material of pole, the stoichiometry of the visual metal used of the amount of oxygen and change.It is used to prepare counterelectrode between different embodiments Processing conditions alterable so that produce it is broad range of may composition (be for example attributed to the aspects such as valence state/oxygen availability Difference).Therefore, describe to obtain or be included in the countless possible oxygen amount in such composite with it, not as coming using " O " Represent that the institute in material is aerobic.Counterelectrode material described herein is suitable for the electrochromic device based on lithium ion. In such device, possible optical transitions are driven using lithium ion, and some lithiums are Irreversible binding in the electrode of such device 's.The visual embodiment of the amount of the lithium of Irreversible binding in electrode and change.Even if in addition, being independent of in electrochromic device In/using lithium ion to drive possible optical transitions in the case of, counterelectrode material described herein also is suitable as counterelectrode material Material.In such embodiment, can be used difference (non-lithium) electric charge carriers, and can make its similarly Irreversible binding in anti- In electrode material.Therefore, in some cases, the stoichiometry of material, institute are described according to " weight " metal ingredient relative ratios It is that, except all metals of (such as) lithium, it there may be in any given embodiment or may not to state " weight " metal ingredient In the presence of.

In certain embodiments, electrochromic device is reversibly circulated between clear state and colored state.Clear In saturating state, current potential is applied to electrochromism lamination 120 so that the made electrochromic material 106 in lamination is in colored shape The available ion of state is resided primarily in counterelectrode 110.When the current potential on electrochromism lamination is inverted, ions across ion is passed Conducting shell 108 is delivered to electrochromic material 106 and material is entered colored state.Hereafter included in the description of Fig. 2 and 3 On being converted to colored state from clear state and the more detailed description of clear state being converted to from colored state, but put up with first Fig. 1 is described in more detail the single layer of lamination 120.

In certain embodiments, all material of composition electrochromism lamination 120 is inorganic, solid (i.e. in solid State) or it is not only inorganic but also solid.Because organic material tends to be degraded with the time, inorganic material is provided can be in extension The advantage of the reliable electrochromism lamination worked in the time period.Also provided without the material being such as in a liquid state in the material of solid-state The receiving usually having and the advantage of leakage problems.The each layer in electrochromic device is discussed in detail below.It will be appreciated that folded Any one or more layers in layer can contain the organic material of a certain amount, but in many implementations, in the layer one It is individual or multiple containing few organic matter or do not contain organic matter.Same situation is applicable to lack in one or more layers Measure the liquid for existing.It should also be clear that can be by the process using liquid component, such as using sol-gel or chemical vapor deposition Some long-pending processes are deposited or otherwise form solid-state material.

Referring again to Fig. 1, voltage source 116 is usually LVPS and can be configured to combine radiation and other environment Sensor carrys out work.Any material with suitable optics, electricity, heat and mechanical property can be used as substrate 102.This Class substrate includes (for example) glass, plastics and specular material.Suitable plastic supporting base includes (for example) acrylic acid, polyphenyl second Alkene, makrolon, allyl diglycol carbonate, SAN (styrene acrylonitrile copolymer), poly- (4-methyl-1-pentene), poly- Ester, polyamide etc..If using plastic supporting base, then well known in such as resin glass field, (such as) eka-gold is preferably used The dura mater of hard rock protective coating, the wear-resistant erosion resisting coating of silica/silicone etc. come plastic supporting base is carried out barrier protection and prevent abrasion.It is suitable The glass of conjunction includes clear or colored soda-lime glass, including sodium calcium float glass.Glass can be to be tempered or be not tempered. In some embodiments of glass (such as soda-lime glass) as the electrochromic device 100 of substrate 102 are used, in substrate In having sodium diffusion-barrier coating (not shown) between 102 and conductive layer 104 to prevent sodium ion from diffusing to conductive layer 104 from glass.

Although substrate 102 can be any size, in some embodiments, it is for about 0.01mm to 10mm thick, excellent Choosing about 3mm to 9mm is thick.

In some embodiments, substrate is building glass.Building glass is the glass as construction material.Building glass Be generally used in commercial establishment, but can also be used for residential building, and generally only may not, by indoor environment with it is outdoor Environment separates.In certain embodiments, building glass is at least 20 inches and multiplies 20 inches, and can be bigger, such as big to about 72 inches multiply 120 inches.It is thick that building glass is generally at least about 2mm.

It is conductive layer 104 on the top of substrate 102.In certain embodiments, one of conductive layer 104 and 114 or Both are inorganic and/or solid.Conductive layer 104 and 114 can be made up of many different materials, including conductive oxide, thin Metal coating, conductive metal nitride and composite conductor.Generally, conductive layer 104 and 114 at least represents by electrochromic layer It is transparent for going out in electrochromic wave-length coverage.Transparent conductive oxide includes metal oxide and doped with one or more The metal oxide of metal.The example of this quasi-metal oxides and blended metal oxide includes indium oxide, tin indium oxide, doping Indium oxide, tin oxide, doped stannum oxide, zinc oxide, aluminum zinc oxide, doping zinc-oxide, ruthenium-oxide, doping ruthenium-oxide etc..One In a little embodiments, the commercially available substrate such as glass substrate contains transparency conducting layer coating.Such product can be used for Both substrate 102 and conductive layer 104.The example of such glass includes Ohio Toledo (Toledo, Ohio's) Pilkington is with trade mark TEC Glass^TMSell and Pittsburgh of Pennsylvania (Pittsburgh, Pennsylvania PPG Industries) are with trade mark SUNGATE^TM300 and SUNGATE^TM500 sell scribble conduction The glass of layer.TEC Glass^TMIt is a kind of glass for scribbling fluorinated tin conductive layer.Equally, such as Gorilla WillowAnd Eagle(each can (Corning, New York) healthy and free from worry from New York Corning, Inc. business Available from) etc. thin glass be also to be suitable for the substrate of electrochromic device described herein.

In some embodiments, two conductive layers (i.e. conductive layer 104 and 114) use identical conductive layer.At some In embodiment, different conductive materials is used in each conductive layer 104 and 114.For example, in some embodiments, TEC Glass are used in substrate 102 (float glass) and conductive layer 104 (fluorinated tin)^TMAnd oxidation is used in conductive layer 114 Indium tin.Using TEC Glass^TMSome embodiments in, have sodium diffuser screen between glass substrate 102 and TEC conductive layers 104 Barrier.

The function of conductive layer be the current potential that voltage source 116 is provided on the surface of electrochromism lamination 120 is diffused to it is folded The interior zone of layer, and almost without ohm potential drop (ohmic potential drop).Will by the electrical connection with conductive layer Current potential is transferred to conductive layer.In some embodiments, (one contacts and another and conductive layer busbar with conductive layer 104 114 contacts) provided between voltage source 116 and conductive layer 104 and 114 and electrically connect.Other conventional meanses be it is also possible to use by conduction Layer 104 and 114 is connected to voltage source 116.

Sheet resistance (the R of conductive layer_s) it is also important, because layer spans relatively large region.In some embodiment party In case, the sheet resistance of conductive layer 104 and 114 is about 1 to 30 ohm every square, or about 5 to 30 ohm every square.In some realities Apply in scheme, the sheet resistance of conductive layer 104 and 114 is about 15 ohm every square.Generally, it is desirable in two conductive layers The sheet resistance of each is roughly the same.In one embodiment, described two layers each have every square about 10-15 ohm Sheet resistance.

Covering conductive layer 104 is cathodic coloration 106 (also referred to as electrochromic layer 106) of layer.In some embodiments In, electrochromic layer 106 is inorganic and/or solid, is in a typical implementation inorganic and solid.Electrochromism Layer can contain any one of many different cathodic coloration electrochromic materials or various, including metal oxide.This eka-gold Category oxide includes (for example) tungsten oxide (WO₃), molybdenum oxide (MoO₃), niobium oxide (Nb₂O₅), titanium oxide (TiO₂), vanadium oxide (V₂O₅) and tantalum oxide (Ta₂O₅).In some embodiments, cathodic coloration doped metallic oxide has one or more doping Thing, such as lithium, sodium, potassium, molybdenum, vanadium, titanium and/or other suitable metals or the compound containing metal.Such dopant can be Cathodic coloration, anodic coloration or non-electrochromic, as long as bulk material is cathodic coloration.For example, some implementations Mixed oxide (such as W-Mo oxides, W-V oxides) is also used in scheme.Electrochromic layer comprising metal oxide 106 can receive the ion from the transfer of counter electrode layer 110.

In some embodiments, tungsten oxide or doped tungsten oxide are used in electrochromic layer 106.In an embodiment In, electrochromic layer is substantially by WO_xIt is made, wherein " x " refers to the atomic ratio of oxygen and tungsten in electrochromic layer, and x is about Between 2.7 and 3.5.Have shown that the tungsten oxide of only substoichiometric shows electrochromism；That is, the tungsten oxide WO of stoichiometry₃ Do not show electrochromism.In a more particular embodiment, using wherein x less than 3.0 and extremely in electrochromic layer Few about 2.7 WO_x.In another embodiment, electrochromic layer is WOx, and wherein x is between about 2.7 and about 2.9.Such as Lu The recognizable oxygen of the technologies such as plucked instrument good fortune backscattering spectrum (Rutherford Backscattering Spectroscopy, RBS) is former The sum of son, including be bonded to the oxygen atom of tungsten and be not bonded to the oxygen atom of tungsten.In some cases, wherein x is 3 or bigger Tungsten oxide layer show electrochromism, this is probably attributed to the tungsten oxide of uncombined excess oxygen and substoichiometric. In another embodiment, tungsten oxide layer has stoichiometry or a greater amount of oxygen, and wherein x is 3.0 to about 3.5.

In certain embodiments, tungsten oxide is crystallization, nanocrystalline or unbodied.In some embodiments, Tungsten oxide is substantially nanocrystalline, and particle diameter be averagely for about 5nm to 50nm as characterized by transmission electron microscopy (TEM) (or about 5nm to 20nm).It is also possible to use x-ray diffraction (XRD) is nanocrystalline by tungsten oxide Morphological Characterization；XRD.Citing comes Say, nanocrystalline electrochromism tungsten oxide can be characterized by following XRD features：About 10 to 100nm (the crystal chis of e.g., from about 55nm It is very little.In addition, nanocrystalline tungsten oxide can show limited long range order, e.g., from about several (about 5 to 20) tungsten oxide structure cells.

The thickness of electrochromic layer 106 depends on the cathodic coloration material selected for electrochromic layer.In some implementations In scheme, for about 50nm of electrochromic layer 106 is to 2,000nm, or about 200nm to 700nm.In some embodiments, it is electroluminescent Photochromic layer is for about 300nm to about 500nm.

In general, in cathodic coloration electrochromic material, the coloring of electrochromic material/colored (or any optics The change of characteristic-such as absorbance, reflectivity and transmissivity) be by the reversible insertion (such as embedded) in ion to material with And the correspondence of charge balance electronics is injected and is caused.Generally, it is responsible for some parts of ion of possible optical transitions by irreversibly beam It is tied in electrochromic material.As be explained below, compensating material is come by the ion of Irreversible binding using some or all of In " blind electric charge ".In most of electrochromic materials, suitable ion includes lithium ion (Li⁺) and hydrogen ion (H⁺) (i.e. matter Son).However, in some cases, other ions are by be adapted to.These ions include (for example) deuterium ion (D⁺), sodium ion (Na⁺), potassium ion (K⁺), calcium ion (Ca⁺⁺), barium ions (Ba⁺⁺), strontium ion (Sr⁺⁺) and magnesium ion (Mg⁺⁺).In this paper institutes In the various embodiments of description, electrochromism phenomenon is produced using lithium ion.(WO in Lithium-ion embeding tungsten oxide_3-y(0<y ≤~0.3)) tungsten oxide is faded to blue (colored state) from transparent (clear state).

Referring again to Fig. 1, in electrochromism lamination 120, the covering electrochromic layer 106 of ion conducting layer 108.Ion is passed It is anodic coloration 110 (also referred to as counter electrode layer 110) of layer on the top of conducting shell 108.In some embodiments, counter electrode layer 110 is inorganic and/or solid.Counter electrode layer serves as ion when can be in clear state comprising that can work as electrochromic device One or more in many different materials of reservoir.Turn in the electrochromism for applying appropriate current potential starting by (such as) During change, some or all of ion transports that anodic coloration counter electrode layer is kept to cathodic coloration electrochromic layer so that Electrochromic layer is set to fade to colored state.Meanwhile, in the case of NiWSnO, counter electrode layer band in the case where ion is lost Color.

In various embodiments, anodic coloration counterelectrode material includes nickel, tungsten, tin and oxygen.The material can be with NiWSnO forms are provided together by any appropriate composition.NiWSnO materials be as anodic coloration material it is particularly useful, because For it is especially clear and for Color Neutral under clear state.Many counterelectrode materials even under its clear state also slightly Micro-strip color (coloring).For example, NiWO generally carries slightly yellow under clear state.For aesthetic reasons, it is preferably electric Cause cathodic coloration and anodic coloration material in color-changing device very clear (transparent) and nothing when device is in clear state Color.Therefore, NiWSnO is the valuable candidate material of anodic coloration counterelectrode material.

NiWSnO can have various compositions when as anodic coloration material.In certain embodiments, can be in NiWSnO Various components between form specific balance.For example, the Ni in material:(W+Sn) atomic ratio can fall about 1:1 and 4:1 Between, such as about 1:1 and 3:Between 1, or about 1.5:1 and 3:Between 1, or about 1.5:1 and 2.5:Between 1, or about 2:1 and 2.5:Between 1.In particular instances, Ni:(W+Sn) atomic ratio is about 2:1 and 3:Between 1.Ni:(W+Sn) atomic ratio It is related to the ratio of the nickle atom in (i) material and the summation of the number of tungsten atom and tin atom in (ii) material.

NiWSnO materials can also have specific W:Sn atomic ratios.In certain embodiments, W:Sn atomic ratios are about 1:9 With 9:Between 1, such as about 1:1 and 3:Between 1, or about 1.5:1 and 2.5:Between 1, or about 1.5:1 and 2:Between 1. In some implementations, specific Ni is used:(W+Sn) atomic ratio and W:Sn atomic ratios.For example, Ni:(W+Sn) atomic ratio Can be about 1:1 and 3:Between 1, wherein W:Sn atomic ratios are about 1:1 and 3:Between 1.In another example, Ni:(W+Sn) atom Than can be about 1.5:1 and 2.5:Between 1, wherein W:Sn atomic ratios are about 1.5:1 and 2.5:Between 1.In another example, Ni: (W+Sn) atomic ratio can be about 2:1 and 2.5:Between 1, wherein W:Sn atomic ratios are about 1.5:1 and 2:Between 1.

Because anodic coloration counter electrode layer 110 containing be used to cathodic coloration electrochromic material be in clear state when The ion of electrochromism phenomenon is produced in cathodic coloration electrochromic material, thus anodic coloration counterelectrode keep it is a large amount of these During ion, anodic coloration counterelectrode preferably has high-transmission rate and neutral color.

When removing electric charge (that is, by ion from anti-by the anodic coloration counterelectrode 110 that regular oxidation nickel tungsten is made from (such as) Electrode 110 is delivered to electrochromic layer 106) when, counter electrode layer will be changed into band brown state from (more or less) pellucidity.Class As, when electric charge is removed from the anodic coloration counterelectrode 110 being made up of NiWSnO, counter electrode layer will be changed into band from pellucidity Brown state.However, the pellucidity of NiWSnO counter electrode layers may be more clear, with more saturating than corresponding NiWO counter electrode layers The few color of bright state (is for example particularly less yellow (low b* color coordinates).

Counterelectrode form can be crystallization, unbodied or its a certain mixture.Crystalline phase can be nanocrystalline.At some In embodiment, nickel-tungsten-tin-oxide (NiWSnO) counterelectrode material is unbodied or substantially unbodied.Have found Various substantially unbodied counterelectrodes are performed better than compared with it crystallizes homologue in some conditions.Can be by using hereafter Some described processing conditions obtain the amorphous state of counterelectrode oxide material.While not wishing to receive it is any theoretical or Mechanism of restriction, but believe in sputter procedure by relatively low energy atom produce unbodied nickel-tungsten oxide or nickel-tungsten- Tin-oxide.For example, in sputter procedure with relatively low target power output, chamber pressure (i.e. relatively low vacuum) higher and/ Or larger source obtains low energy atom with substrate distance.Amorphous membrance is also more likely formed, wherein in the presence of relatively high score The heavy atom (such as W) of number/concentration.Under described process conditions, produce has more preferable stability under UV/ heat exposures Film.Substantially unbodied material can be with some crystallizations, and generally but not one is set to the nanometer being dispersed in [amorphous Brilliant material.The crystallite dimension and amount of such crystalline material are more fully hereinafter described.

In some embodiments, the form of counterelectrode may include crystallite, nanocrystalline and/or amorphous phase.For example, Counterelectrode can be (for example) have the material for wherein spreading all over the [amorphous for having nanocrystal.In certain embodiments, receive Meter Jing Ti composition counterelectrode material about 50% or lower, about the 40% or lower of counterelectrode material, the pact of counterelectrode material 30% or lower, about the 10% or lower of about 20% or lower or counterelectrode material of counterelectrode material is (depending on embodiment It is fixed by weight or by volume).In certain embodiments, the maximum gauge of nanocrystal is less than about 50nm, in some feelings Under condition less than about 25nm, less than about 10nm or less than about 5nm.In some cases, the average diameter of nanocrystal is for about 50nm Or it is smaller, or about 10nm or smaller, or about 5nm or smaller (e.g., from about 1-10nm).In certain embodiments, it is desirable to one Nanocrystal size is distributed, and wherein at least about 50% nanocrystal has with average nanocrystal diameter deviation in 1 standard Diameter within deviation, such as wherein at least about 75% nanocrystal has with average nanocrystal diameter deviation in 1 mark Diameter or wherein at least about 90% nanocrystal within quasi- deviation have with average nanocrystal diameter deviation in 1 standard Diameter within deviation.It has been found that compared with the counterelectrode of relatively polycrystalline, including the counterelectrode of [amorphous tends to More efficiently work.In certain embodiments, additive can form host matrix, and basic anodic coloration material can be found wherein The farmland of material.

In all cases, host matrix is substantially unbodied.In certain embodiments, it is unique in counterelectrode Crystalline texture is formed by the basic anodic coloration electrochromic material in (such as) oxide form.As mentioned, additive can Help to be formed not essentially crystalline amorphous host matrix, but the host matrix to incorporate basic anodic coloration electroluminescent The farmland (being for example in some cases nanocrystal) of off-color material.In other embodiments, additive and anodic coloration base Plinth material forms chemical compound by covalent and/or ionic bonding together.The compound can be crystallization, unbodied Or its combination.In other embodiments, anodic coloration basic material forms the farmland of wherein additive with discrete phase or the shape of capsule The host matrix that formula is present.For example, some embodiments include the amorphous anti-of the [amorphous with the first material Electrode, wherein the second material (also for unbodied) with capsule (such as herein for the crystallization material being distributed in [amorphous The capsule of the described diameter of material) form be dispersed throughout in the first material.

In some embodiments, the thickness of counterelectrode is for about 50nm to about 650nm.In some embodiments, anti-electricity The thickness of pole is for about 100nm to about 400nm, sometimes in the range of about 150nm to 300nm, or about 200nm to 300nm it Between.The thickness of counter electrode layer 110 is also substantially homogeneous.In one embodiment, substantially homogeneous counter electrode layer exists Change only about ± 10% in each in foregoing thickness ranges.In another embodiment, substantially homogeneous counter electrode layer Change only about ± 5% in each in foregoing thickness ranges.In another embodiment, substantially homogeneous counter electrode layer Change only about ± 3% in each in foregoing thickness ranges.

In being maintained at counter electrode layer during clear state (and electrochromism is accordingly maintained at during colored state In layer) and can be used for the amount of the ion for driving electrochromism transformation depending on the composition of layer and thickness and the making side of layer Method.Electrochromic layer can support the millicoulomb human relations of layer surface area every square centimeter tens with counter electrode layer in adjacent area (millicoulomb) charge available (in lithium ion and the form of electronics).The charge capacity of electrochromic film is by applying The amount of electric charge that the film of external voltage or current potential per unit area and unit thickness can reversibly be loaded and unloaded.In a reality In applying scheme, WO₃Layer has about 30mC/cm²/ micron and about 150mC/cm²Charge capacity between/micron.In another embodiment party In case, WO₃Layer has about 50mC/cm²/ micron and about 100mC/cm²Charge capacity between/micron.In an embodiment In, NiWSnO layers has about 75mC/cm²/ micron and about 200mC/cm²Charge capacity between/micron.In another embodiment In, NiWSnO layers has about 100mC/cm²/ micron and about 150mC/cm²Charge capacity between/micron.

Between electrochromic layer 106 and counter electrode layer 110, generally there is ion conducting layer 108.Ion conducting layer 108 exists Electrochromic device serves as the medium of conveying ion (in the way of electrolyte) when being converted between clear state and colored state. Preferably, ion conducting layer 108 is high conduction to the relevant ions of electrochromic layer and counter electrode layer, but with very low Electronic conductivity so that the electro transfer for occurring during normal operation is negligible.With high ionic conductivity it is thin from Sub- conducting shell (also sometimes referred to as electrode layer) is permitted quick ionic conduction and therefore permits being switched fast realizing High performance electrochromic device.In certain embodiments, ion conducting layer 108 is inorganic and/or solid.By certain One material and to produce relatively fewer defect in the way of to make when, electrode layer can be made very thin to produce High performance device.In various embodiments, ionic conductor material has about 10⁸Siemens (Siemen)/cm or ohm^- ¹cm^-1With about 10⁹Siemens/cm or ohm^-1cm^-1Between ionic conductivity and about 10¹¹The electronic resistance of ohm-cm.

In other embodiments, electrode layer can be saved.In such embodiment, electrochromism to be used for being formed During the electrochromism lamination of device, single ionic conductor material is not deposited.But, in these embodiments, can be with anode Counterelectrode material direct physical contact is coloured to deposit cathodic coloration electrochromic material.Can deposition anode coloured material and negative electrode One or both in coloured material is in a ratio of oxygen-enriched part with including the remainder with material.Generally, oxygen-rich fraction with Other kinds of layer contact.For example, electrochromism lamination may include the anodic coloration material with cathodic coloration material, Wherein cathodic coloration material includes the oxygen-rich fraction with anodic coloration material direct physical contact.In another example, electroluminescent change Color lamination includes the anodic coloration material with cathodic coloration material, and wherein anodic coloration material includes and cathodic coloration material The oxygen-rich fraction of direct physical contact.In another example, anodic coloration material all includes oxygen-rich fraction with cathodic coloration material, The wherein oxygen-rich fraction direct physical contact of the oxygen-rich fraction of cathodic coloration material and anodic coloration material.

Can be provided in the form of different sublayers these layers oxygen-rich fraction (such as negative electrode or anodic coloration material include it is oxygen-enriched Sublayer and less oxygen-enriched sublayer).Oxygen-rich fraction (such as negative electrode or anodic coloration material of the layer can be also provided in hierarchical layer Material may include the gradient of oxygen concentration, and the gradient is being orthogonal on the direction on the surface of the layer).Enter in following United States Patent (USP) One step is discussed and saves electrode layer and anodic coloration counterelectrode material and cathodic coloration electrochromic material directly contact Each of embodiment, described patent are incorporated herein in entirety by reference：U.S. Patent number 8,300,298 and U.S. State's patent No. 8,764,950.

The embodiment of Fig. 1 is back to, the example for being suitable for the material of lithium ion conductor layer includes lithium metasilicate, lithium metasilicate Aluminium, lithia, tungstate lithium, lithium borate aluminium, lithium borate, lithium metasilicate zirconium, lithium niobate, lithium borosilicate, phosphorus lithium metasilicate, lithium nitride, oxygen Lithium nitride, lithium fluoride aluminium, LiPON (LiPON), lithium titanate lanthanum (LLT), lithia tantalum, lithia zirconium, lithium siloxicon nitrogen (LiSiCON), lithium phosphate titanium, lithia germanium vanadium, lithia zinc germanium and permission lithium ion are passed therethrough while having high resistance Other ceramic materials of (preventing electronics from being therefrom moved through).However, any material all can be used for ion conducting layer 108, premise Condition be it can be made into low ratio of defects and it allow ion counter electrode layer 110 to electrochromic layer 106 it Between transmission simultaneously substantially prevent electronics from passing through.

In certain embodiments, ion conducting layer is crystallization, unbodied or its mixture.Generally, ionic conduction Layer is unbodied.In another embodiment, ion conducting layer is nanocrystalline.In another embodiment, ionic conduction Layer is the amorphous and crystalline phase of mixing, and wherein crystalline phase is nanocrystalline.

Ion through ion conducting layer conveying between electrochromic layer and counter electrode layer is electroluminescent to be resided at it Realize that color change (that is, makes electrochromic device be changed into colored shape from clear state in electrochromic layer when in photochromic layer State).For the device with anodic coloration counter electrode layer, lacking these ions can produce color in counter electrode layer.Depending on electroluminescent Depending on the material selection of color-changing device lamination, such ion includes lithium ion (Li⁺) and hydrogen ion (H⁺) (i.e. proton).As above It is previously mentioned, other ions can be used in certain embodiments.These ions include deuterium ion (D⁺), sodium ion (Na⁺), potassium from Son (K⁺), calcium ion (Ca⁺⁺), barium ions (Ba⁺⁺), strontium ion (Sr⁺⁺) and magnesium ion (Mg⁺⁺).In certain embodiments, Hydrogen ion is not used, because the side reaction during device works causes in conjunction with into hydrogen, hydrogen may escape simultaneously from device And make performance degradation.Therefore, the ion without this problem, such as lithium ion can be used.

Electrochromic device 100 may include one or more additional layers (not shown), such as one or more passive layers.Electricity Cause to may include to improve the passive layer of some optical characteristics in color-changing device 100.Use is may also include in electrochromic device 100 In the passive layer for providing moistening or scraping resistance.For example, can use at anti-reflective or protective oxide or nitride layer Reason conductive layer.Other passive layers may be used to gas-tight seal electrochromic device 100.

Electrochromic material can contain blind electric charge.Blind electric charge in electrochromic material is such electric charge (such as in oxygen Change tungsten electrochromic material in the case of be negative electrical charge), its making when be present in material, by the ion of oppositely charged or its He compensates electric charge carrier.For example, in the case of tungsten oxide, during the value of blind electric charge depends on the sputtering of tungsten oxide Superfluous oxygen concentration.Functionally, it is necessary to can effectively change electrochromism material in the ion for converting electrochromic material The blind electric charge of precompensation of the optical characteristics of material.In the case where blind electric charge is not compensated in advance, supplied to electrochromic material from Son irreversibly will be merged into material, and optical states to material do not work.Therefore, usually electrochromic device The ion (such as lithium ion or proton) of q.s is provided to compensate blind electric charge and provide a collection of for reversibly making electroluminescent change The ion that color material switches between two kinds of optical states.In many known electrochromic devices, electric charge is compensating blind electricity Lost in the first electrochemistry circulation of lotus.

In some embodiments, there is the lithium of q.s in electrochromism lamination 120 come in compensating electrochromic layer 106 Blind electric charge, and then exist in lamination 1.5 to 2.5 times of amount that are about used for compensating blind electric charge of additional quantity lithium (with Quality meter) (initially in such as counter electrode layer 110).In other words, it is necessary to about 1.5 to 2.5 times of lithium amount is compensated for electricity The blind electric charge of the Reversible Cycle between electrochromic layer 106 and counter electrode layer 110 in mutagens color lamination 120.In some implementations In scheme, there are enough lithiums in electrochromism lamination 120 to compensate the blind electric charge in electrochromic layer 106, then counterelectrode There is the amount (in mass) for being about this amount twice in the other places in layer 110 or lamination.

In some embodiments, electrochomeric glass is integrated into insulating window unit (IGU).Insulating window unit It is made up of the more glass sheets for being assembled into a unit, is generally intended to maximize contained gas in the space formed by the unit The insulative properties of body, while providing clear sight through the unit.Except for electrochomeric glass to be connected into voltage Outside the electrical lead in source, incorporate electrochomeric glass insulating window unit will be similar to that it is currently known heat-insulated in this area Glass unit.The higher temperature that may be experienced due to electrochromism insulating window unit (is attributed to electrochomeric glass absorption Radiation energy), than the more robust fluid sealant of fluid sealant used in conventional thermal barrier glass unit may be necessary.Lift For example, stainless steel spacer bar, high temperature polyisobutene (PIB), the road fluid sealants of Xin bis-, the paper tinsel coating for spacer bar seam PIB adhesive tapes etc..

The method for making electrochromic

The deposition of electrochromism lamination

As being previously mentioned in general introduction above, the one side of embodiment herein is to make the side of electrochromic Method.In a broad sense, methods described be included on substrate be sequentially deposited (i) cathodic coloration electrochromic layer, (ii) it is optional from Sub- conducting shell and (iii) anodic coloration counter electrode layer are forming lamination.The sequential aggradation is using with controlled surrounding's ring The single integration depositing system in border, pressure is controlled in the surrounding environment independently of the external environment condition outside depositing system is integrated Power, temperature and/or gas composition, and substrate is in the sequential aggradation phase of electrochromic layer, ion conducting layer and counter electrode layer Between whenever will not all leave the integration depositing system.(be hereafter more fully described with regard to Fig. 8 A-E the week for remaining controlled The example of the integration depositing system in collarette border).Gas composition can by the partial pressure of the various components in controlled surrounding environment come Characterize.Controlled surrounding environment can also be characterized by granule amount or density of particle.In certain embodiments, around controlled Environment contains every cubic metre less than 350 particulates (size is 0.1 micron or bigger).In certain embodiments, controlled week Collarette border meets the requirement of class 100 clean room (US FED STD 209E).In certain embodiments, controlled surrounding environment Meet 10 grades of requirements of toilet (US FED STD 209E).Substrate can enter and/or leave satisfaction 1000 grades, 100 grades or very Controlled surrounding environment into 10 grades of toilets of requirement.

It is generally but not certain, this kind of preparation method is integrated into for manufacturing electroluminescent change as substrate using building glass In the multistep process of color window.For convenience, below description covers methods described with it for making electrochromic Various embodiments in the situation of multistep process, but method not limited to this herein.Can be used more described herein Or all of operation makes EC mirror and other devices with method.

Fig. 2 be according to such as with regard to the multistep process described by Fig. 4 electrochromic device 600 cross-sectional view.Fig. 4 exhibitions Show that description makes the technological process of the method 700 of the electrochromic for incorporating electrochromic device 600.Fig. 3 is device 600 Top view, show the position of the groove in cut-in device.Therefore, Fig. 2-B and Fig. 4 will be described together.This specification One side be the electrochromic for including device 600, and the another aspect of this specification be make include the electricity of device 600 Cause the method 700 of color-changing window.Below description includes the description of Fig. 5-7.Fig. 5-7 illustrates made as device 600 The specific method of the electrochromism lamination for dividing.

Fig. 2 shows the instantiation of electrochromic device 600, and the electrochromic device is from the lining being made up of glass Bottom 605 proceeds by making, and the substrate is optionally saturating with the coating of diffusion barrier 610 and in the diffusion barrier first Bright conductive oxide (TCO) coating 615.The substrate that method 700 is used is (such as) float glass, its have sodium diffusion barrier and Anti-reflecting layer and followed by transparency conducting layer (such as transparent conductive oxide 615).As mentioned above, suitable substrate Pilkington including Ohio Toledo is with trade mark TECSale and the PPG of Pittsburgh of Pennsylvania Industries is with trade mark300 and500 glass sold.First tco layer 615 is for being formed First in two conductive layers of the electrode of the electrochromic device 600 made on substrate.

Method 700 is since cleaning process 705, wherein cleaning substrate is so that it is ready for following process.Various realities An example for applying the suitable cleaning process in scheme and equipment is Lisec^TM(it is purchased from Austrian Sai Tengshitaiteng The glass cleaning equipment and the trade mark of method of the LISEC Maschinenbau Gmbh of (Seitenstetten, Austria) Name).

Cleaning substrate may include mechanical scrub and ultrasonically treated regulation to remove undesired particulate.As mentioned, it is micro- Grain may result in the partial short-circuit in surface blemish and device.

After substrate is cleaned, first laser scoring process 710 is carried out to remove the tco layer of a line first on substrate. In one embodiment, gained groove cuts through TCO and diffusion barrier and (but does not penetrate diffuser screen substantially in some cases Barrier).Fig. 2 illustrates this first laser delineation groove 620.In the substrate ditch is depicted across the whole length of the side of substrate So as to the TCO regions of an adjacent edges at isolation liner bottom, it finally will be contacted groove with the first busbar 640, the busbar For providing electric current to the second tco layer 630, second tco layer is deposited on electrochromism (EC) lamination 625 (as retouched above State, it includes electrochromic layer, ion conducting layer and counter electrode layer) top on.

Fig. 3 schematically shows the position of (not in scale) groove 620.In the embodiment for being shown, diffuser screen (main) part that is not isolated from of the first tco layer on barrier finally contacts with the second busbar 645.Isolated groove 620 may be needed, Because in certain embodiments, the method that the first busbar is attached to device is included laying in device stack layer (the In the major part of the isolated part of one tco layer and the first tco layer) it is pressed into through described device stack layer afterwards.Ability Field technique personnel will be recognized that in electrochromic device electrode (being in this case tco layer) provide electric current its He is arranged as possible.The TCO regions for delineating isolation by first laser are usually along the region at edge of substrate, institute Stating region will finally together with busbar when being incorporated into and integrating in glass unit (IGU) and/or glass pane plate, framework or curtain wall It is hidden.Laser generally but not one for first laser delineation is set to pulse type laser, such as diode-pumped solid state laser. For example, can be used from IPG Photonics (Massachusetts Oxford (Oxford Massachusetts)) or come from The suitable laser of Ekspla (Lithuania Vilnius (Vilnius Lithuania)) carries out laser grooving and scribing.

After first laser delineation 710, substrate is necessarily generally but not cleaned again using ablution as described above (operation 715).This second cleaning process is carried out to remove any chip caused by first laser delineation.Complete clean operation After 715, substrate is ready for the deposition of EC laminations 625.This is shown as process 720 in technological process 700.Such as institute above Mention, methods described includes being sequentially deposited on substrate using the single integration depositing system with controlled surrounding environment I EC layers of () cathodic coloration, (ii) optional IC layers and CE layers of (iii) anodic coloration are (such as in various embodiments NiWSnO) to form the wherein IC layers of lamination for separating EC layers with CE interlayers, deposited independently of integration in the surrounding environment The external environment condition of its exterior comes control pressure and/or gas composition, and substrate is heavy in EC layers, IC layers and CE layers of order Whenever integration depositing system will not be left during product.

In one embodiment, each in the layer of sequential aggradation is physical vapour deposition (PVD).In general, can lead to Various technologies are crossed to deposit the layer of electrochromic device, including physical vapour deposition (PVD), chemical vapor deposition, plasma enhancing Vapour deposition and ald are learned, only lists a little.Physical vapour deposition (PVD) is including in this area as the term is employed herein The gamut of the PVD technique for being understood, including sputtering, evaporation, ablation etc..Fig. 5 illustrates an embodiment party of process 720 Case.First, on substrate deposit EC layer of cathodic coloration (process 722), then deposition IC layers (process 724) (it is as noted above, In certain embodiments, IC layers is saved, and therefore saves process 724), then deposition anode colours CE layers (process 726). The deposition of reversed sequence is also embodiment, i.e. wherein deposits CE layers first, then deposits optional IC layers, and then sink EC layers of product.In one embodiment, each in electrochromic layer, optional ion conducting layer and counter electrode layer is solid Phase layer.In another embodiment, each in electrochromic layer, optional ion conducting layer and counter electrode layer only includes Inorganic material.

Although it will be appreciated that some embodiments are carried out according to counter electrode layer, electrode layer and electrochromic layer Description, but any one or more in these layers can be made up of one or more sublayers, and one or more of sublayers can have By it is different constitute, size, form, charge density, optical characteristics etc..In addition, any one or more in the layer of device can With classification composition or classification form, wherein the composition or form change at least a portion of the thickness of layer respectively. In one example, the concentration of oxygen, dopant or electric charge carrier changes in given layer, at least when the layer is made.Another In one example, the form of layer changes to amorphous from crystallization.Can such classification composition or form be selected to influence device Functional characteristic.In some cases, additional layer can be added to the lamination.In an example, heat dissipating layer is inserted in one Between individual or two tco layers and EC laminations.

Additionally, as described above, the electrochromic device of some embodiments is utilized via ion conducting layer electroluminescent Ion movement between photochromic layer and counter electrode layer.In some embodiments, these ions (or its neutral precursor) are with final One or more layers in embedded lamination are introduced into lamination (following article is more fully described with regard to Fig. 6 and Fig. 7).In some embodiment party In case, one or more in these ions and electrochromic layer, ion conducting layer and counter electrode layer are introduced into lamination simultaneously. Wherein using an embodiment of lithium ion in, by lithium (such as) with for manufacturing the material of one or more in stack layer Material is sputtered or sputtered as a part for the material including lithium (such as by the method using lithiated nickel dioxide tungsten tin) together. In one embodiment, IC layers is deposited via being sputtered to lithia sial target.In another embodiment, by Li and silicon Aluminium is cooperatively sputtered to realize desired film.

Referring again to the process 722 in Fig. 5, in one embodiment, deposition electrochromic layer includes deposition WO_x. In one embodiment, deposition electrochromic layer includes sputtering tungsten from the target of tungstenic.In such embodiment, gold is used Category tungsten (or tungsten alloy) target.In another embodiment (it can also use metal tungsten target), sputter gas be inert gas (for example Argon or xenon), wherein in the presence of some oxygen-containing gas (such as molecule or elemental oxygen).This is to may be present in the deposition chamber in bigger chamber Or a part for the controlled surrounding environment in station.

In one embodiment, for the sedimentation rate of regular tungsten, too high work(is avoided the need for using multiple targets Rate (or other the improper adjustment to wanted process conditions) improves sedimentation rate.The distance between target and substrate are likely to attach most importance to Want.In one embodiment, target (negative electrode or source) to the distance between substrate surface between about 35mm and about 150mm； In another embodiment, between about 45mm and about 130mm；And in another embodiment, in about 70mm and about 100mm Between.

Although it will be appreciated that EC layers of deposition is described according to from target sputtering, it is used in some embodiments His deposition technique.For example, can be using chemical vapor deposition, ald etc..As known in the art, these Each of technology has the material source form of their own together with PVD.

Referring again to Fig. 5, operation 724, once deposited EC layers, can deposit optional IC layers.

Referring again to Fig. 5, operation 726 after IC layers of deposition, deposits CE layers.In one embodiment, anti-electricity is deposited Pole layer includes the layer of deposition nickel-tungsten-tin-oxide (NiWSnO).In a specific embodiment, deposition counter electrode layer includes The target including the tungsten of about 30% (by weight) to about 70% in nickel is sputtered in an oxygen-containing environment produce nickel tungsten tin oxygen (tin by the tungsten in the nickel target for suitably constituting by being provided, or is provided by another target, or the tin by such as evaporating for the layer of compound Another source in source provides).In another embodiment, target is the tungsten in nickel between about 40% and about 60%, in another embodiment party It is the tungsten in nickel between about 45% and about 55% in case, and is in yet another embodiment in nickel about 51% tungsten.

During anodic coloration counter electrode layer includes some embodiments of NiWSnO wherein, many deposition targets or target can be used Combination.For example, the single metal target of nickel, tungsten and tin can be used.In other cases, at least one of target includes Alloy.For example, the alloys target of nickel-tungsten can be used together with metal tin target.In another case, the alloys target of ni-sn can It is used together with metal tungsten target.In another case, the alloy of tungsten-tin can be used together with metallic nickel target.In still other cases, The alloys target containing nickel-tungsten-tin material can be used.Additionally, any one of listed target can be provided in the form of an oxide. Generally, generation in the presence of oxygen is sputtered at, and such oxygen is integrated into material.Alternatively or except oxygen-containing sputtering gas Outside atmosphere, oxygen containing sputtering target is it is also possible to use.

Sputtering target for forming anodic coloration counterelectrode material can have permits counterelectrode with composition described herein Any one of come the composition that is formed.Wherein using in an example of single sputtering target, sputtering target can have and this paper institutes The composition of the composition matching of any one of disclosed NiWSnO materials.In other instances, using the combination of sputtering target, and Combining the composition of target allows to be deposited with any one of NiWSnO materials disclosed herein.In addition, following article enters one Step is discussed, and can permit depositing when needed any mode of the material to arrange sputtering target.Metallic target is typically to be present Or in the absence of inert gas (such as argon) in the case of sputtered in oxygen.Metal oxide target is typically in independent indifferent gas Sputtered in body.Ni, W and Sn metallic target, NiW targets and Sn targets, NiWO targets and tin oxide target etc. can be used.It is various to be combined as It is possible.As another example, if necessary to single target, then can be used the nickel tungsten tin alloy target with appropriate composition or NiWSnO targets.

In one embodiment, the oxygen that the gas composition for being used when CE is formed contains between about 30% and about 100%, In another embodiment containing oxygen between about 80% and about 100%, in yet another embodiment containing about 95% with about Oxygen between 100%, contains about 100% oxygen in another embodiment.In one embodiment, for being carried out to CE targets The power density of sputtering is in about 2 watts/cm²With about 50 watts/cm²Between (based on applied power divided by target surface area And determine)；In another embodiment in about 5 watts/cm²With about 20 watts/cm²Between；And exist in yet another embodiment About 8 watts/cm²With about 10 watts/cm²Between；It is for about in another embodiment 8 watts/cm².In some embodiments, It is provided as realizing the power of sputtering and delivering via direct current (DC).In other embodiments, reacted using pulse DC/AC Sputtering.Wherein using pulse DC/AC reactive sputterings an embodiment in, frequency between about 20kHz and about 400kHz, In another embodiment between about 20kHz and about 50kHz, in yet another embodiment about 40kHz and about 50kHz it Between, for about 40kHz in another embodiment.Pressure in deposition station or room is in one embodiment in about 1 millitorr (mTorr) and about 50 millitorrs between, in another embodiment between about 20 millitorrs and about 40 millitorrs, in another embodiment In between about 25 millitorrs and about 35 millitorrs, for about 30 millitorrs in another embodiment.In some cases, with (such as) argon Nickel-tungsten oxide NiWO ceramic targets are sputtered with oxygen.In one embodiment, NiWO is in about 15% (atom) Ni and about 60% Between Ni；Between about 10%W and about 40%W；And between about 30%O and about 75%O.In another embodiment, NiWO is between about 30% (atom) Ni and about 45%Ni；Between about 10%W and about 25%W；And in about 35%O and about Between 50%O.In one embodiment, NiWO is for about 42% (atom) Ni, about 14%W and about 44%O.In certain situation Lower NiWO targets can be used in combination with tin or tin oxide target.In another embodiment, deposition counter electrode layer is included counter electrode layer Thickness of the deposition extremely between about 150nm and 350nm；It is for about in yet another embodiment 200nm to about 250nm thick.Above-mentioned bar Part can use to realize high-quality NiWSnO layers deposition each other with any combinations.

Sputter procedure for forming CE layers can utilize one or more sputtering targets.One the one of sputtering target is used wherein In individual example, the target may include nickel, tungsten and tin.In some cases, sputtering target also includes oxygen.Sputtering target may include grid Or other overlapping shapes, wherein including different associated materials, (some parts of such as grid may include the different piece of grid Elemental nickel, elemental tungsten, element tin, nickel-tungsten, nickel-tin alloy and/or tungsten-tin alloy).In some cases, sputtering target can It is the alloy of associated materials (such as in nickel, tungsten and tin both or more person).Using two or more sputtering targets In the case of, each sputtering target may include one of associated materials (nickel of such as element and/or alloy form, tungsten and/or tin, It is therein any one can provide in the form of an oxide).Sputtering target can be overlapped in some cases.In some embodiments, splash Shoot at the target also rotatable.As noted, counter electrode layer is usually oxide material.Oxygen can be used as sputtering target and/or sputter gas A part is provided.In some cases, sputtering target is substantially simple metal, and sputtered in the presence of oxygen with Form oxide.

In one embodiment, for regular CE layers sedimentation rate, avoided the need for using multiple targets too high Power (or other the improper adjustment to wanted process conditions) improves sedimentation rate.In one embodiment, CE targets (negative electrode Or source) and the distance between substrate surface between about 35mm and about 150mm；In another embodiment in about 45mm and about Between 130mm；And in another embodiment between about 70mm and about 100mm.

As noted, one or more rotary targets can be used in some cases.In all cases, rotary target may include Internal magnets.Fig. 9 A present the view of rotary target 900.The inside of rotary target 900 is magnet 902, and the magnet (is supplied to target During appropriate electric power) make material in sputtering cone 906 (sputtering cone is also sometimes referred to as sputter plasma) from target surface 904 Sputter out.Magnet 902 can extend along the length of sputtering target 900.In various embodiments, magnet 902 can be oriented Extend radially outwardly so that gained sputter cone 906 along the surface 904 for being orthogonal to target direction (direction be along The central shaft for sputtering cone 906 is measured, and the central shaft generally corresponds to sputter the mean direction of cone 906) from sputtering Target 900 is distributed.Sputtering cone 906 can be v-shaped when viewed from above, and can be along height (or the magnet 902 of target 900 Height, if highly not identical with target 900) extend.Magnet 902 inside rotary target 900 can be fixed (although i.e., The surface 904 of target 900 rotates, but magnet 902 in target 900 does not rotate) so that sputtering cone 906 is also for fixed.It is showed in Institute's sputter material that a small circle/representative in sputtering cone 906 is distributed from sputtering target 900.When needed can by rotary target with Other rotary targets and/or flat target are combined.

In an example, EC layers of NiWSnO anodic colorations are deposited using two rotary targets：Including nickel and tungsten first Target and the second target including tin (any one or both is optionally in oxide form).Fig. 9 B are presented for sinking in this way The top-down view of the depositing system of product anodic coloration layer.Nickel tungsten target 910 and tin target 912 each include internal magnets 914. The angulation toward each other of magnet 914 so that the sputtering cone 916 and 918 respectively from nickel tungsten target 910 and tin target 912 is overlapped.Fig. 9 B Also show the substrate 920 above passed through in target 910 and 912.As illustrated, sputtering cone 916 and 918 clashes into substrate at it 920 parts are closely overlapped.In some embodiments, the sputtering cone from various sputtering targets can be overlapped closely to each other (such as the Non-overlapping Domain that only single sputtering cone is reached when being deposited on substrate is less than total area that any sputtering cone is reached About the 10% of domain, for example, less than about 5%).In other embodiments, sputtering cone can offset with one another more so that splash The non-overlapped area of any one of pencil body or both with the gross area reached for any sputtering cone at least about 10%, For example, at least about 20%, or at least about 30%, or at least about 50%.

In the embodiment similar with the embodiment shown in Fig. 9 B, a sputtering target is tungsten, and another is nickel With the alloy (any one or two targets are optionally in oxide form) of tin.Similarly, a sputtering target can be nickel, and another It can be the alloy (any one or two targets are optionally in oxide form) of tungsten and tin.In the relevant embodiments, three are used Sputtering target：Tin target, nickel target and tungsten target (any of which is optionally in oxide form).It is every in from three targets The sputtering cone of one can be overlapped by making magnet angulation in due course.Additionally, shielding, grid and/or other volumes can be used Outer plasma shaping element helps to produce appropriate plasma mixture to form NiWSnO.

In the submission of on May 2nd, 2012 and the U.S. Patent Application No. of entitled " ELECTROCHROMIC DEVICES " Various sputtering target designs, orientation and embodiment, the side that this application is quoted in full are further discuss in 13/462,725 Formula is incorporated herein.

The density and orientation/shape of the material sputtered from sputtering target depend on various factors, including (such as) is used to Produce the magnetic field shape and intensity, pressure and power density of sputter plasma.The distance between adjacent target and each The distance between target and substrate are likely to influence how sputter plasma will mix and how resulting materials are deposited on lining On bottom.

In certain embodiments, there is provided two distinct types of sputtering target is single in electrochromism lamination to deposit Layer：A () main sputtering target, it is by sputtering of materials to substrate, and (b) auxiliary sputtering target, and it is by sputtering of materials to main sputtering target. Main sputtering target and auxiliary sputtering target may include the oxidation of the metal that realization to be constituted in the layer for being deposited, metal alloy and metal Any combinations of thing.In a particular instance, main sputtering target includes the alloy of nickel and tungsten, and auxiliary sputtering target includes tin.Another In one example, main sputtering target includes tin, and auxiliary sputtering target includes the alloy of nickel and tungsten.These sputtering targets can be used together to sink Product NiWSnO anodic coloration layers.It is also possible to use other combinations of alloy (such as ni-sn, tungsten-tin) and metal (such as nickel, tungsten). Any sputtering target can be provided in the form of the oxide.

When using both major-minor sputtering target and auxiliary sputtering target, it is many it is different be set to it is possible.Figure 10 A and Figure 10 B Present a top-down view for embodiment of the deposition station for depositing NiWSnO anodic coloration counter electrode layers.Though So presented in the particular condition of deposition NiWSnO, but it is folded to deposit electrochromism to can be used sputtering target discussed herein to configure Layer in any material, precondition be target have be used to deposit the appropriate composition for wanting material in lamination.Main sputtering is provided Target 1001 and auxiliary sputtering target 1002, it each has internal magnets 1003.Each sputtering target is rotatable sputtering in this example Target, but the target of plane or other shapes also can be used.Target can rotate in the same direction or in the opposite direction.Such as Figure 10 A Shown in, when not existing substrate 1004 between described two targets, auxiliary sputtering target 1002 is by sputtering of materials to main sputtering target On 1001.This deposits to main sputtering target 1001 material from auxiliary sputtering target 1002.Then, as shown in Figure 10 B, in lining When bottom 1004 is moved to the position between two targets, stopping is sputtered from auxiliary sputtering target 1002, and beginning is splashed from main sputtering target 1001 It is incident upon on substrate 1004.

When sputtering out and depositing to substrate 1004 material from main sputtering target 1001, the material for being deposited includes It is originated from the material of both main sputtering target and auxiliary sputtering target 1001 and 1002.In fact, this kind of method is related in main sputtering target The sputtering target surface that mixes on 1001 is formed in situ.One advantage of this kind of method is on the surface of main sputtering target 1001 (for example this kind of material is tin, tungsten, nickel or its combination in some cases periodically to deposit the material from auxiliary sputtering target 1002 And/or alloy) fresh coating.Then the material for mixing is delivered together to substrate 1004.

In fig 1 oc in shown related embodiment, auxiliary sputtering target 1022 is located at behind main sputtering target 1021, and is served as a contrast Bottom 1024 is passed through before main sputtering target 1021 so that it will not stop the sight line between two targets 1021 and 1022.Sputtering target In each may include magnet 1023.In this embodiment, without periodically stopping being sputtered onto from auxiliary sputtering target 1021 On main sputtering target 1022.But, such sputtering can continuously occur.Substrate 1024 and auxiliary sputtering target are located in main sputtering target 1021 Between 1022 (such as without sight line between auxiliary sputtering target 1022 and substrate 1024) in the case of, main sputtering target 1021 will rotate, So that deposition to the material on main sputtering target 1021 can be sputtered onto on substrate 1024.Have more in the design of auxiliary sputtering target 1022 Many flexibilities.In the relevant embodiments, auxiliary sputtering target can be plane or other non-rotating targets.In two rotary targets of use In the case of, target can rotate in the same direction or in the opposite direction.

In similar embodiment, auxiliary sputtering target (such as the auxiliary target in Figure 10 A to Figure 10 C) can be replaced with another auxiliary material material source Change.Auxiliary material material source can be provided to main sputtering target material by means in addition to sputtering.In an example, auxiliary material material source will The material of evaporation is provided to main sputtering target.The material of evaporation can be any component of layer for being deposited.In various examples, evaporation Material be metal element or metal oxide.The particular instance of the material of evaporation includes tin, tungsten and nickel, and it can be used to be formed NiWSnO anodic coloration counterelectrode materials.In one embodiment, by element tin be evaporated to include nickel and tungsten mixture and/ Or on the main sputtering target of alloy.It is a kind of material of particularly preferred evaporation that tin is attributed to its relatively low fusing point.In auxiliary material material source In the case that the material of evaporation is provided, auxiliary material material source can be provided at relative to any position of main sputtering target and substrate.One In a little embodiments, there is provided auxiliary material material source so that it is behind main sputtering target and is mainly deposited on main sputtering target, with figure Setting shown in 10C like.

In the case where both main sputtering target and auxiliary sputtering target is used, can (it be the moon in the current potential with main sputtering target Pole) it is in a ratio of under the current potential of negative electrode and operates auxiliary sputtering target.Or, the target can be operating independently.Additionally, no matter relative target How is current potential, will be deposited on main target from the neutral substance of auxiliary target injection.Neutral atom will be the part of flux, and they will Be deposited on the main target of negative electrode, but regardless of relative potentials how.

In various embodiments, reactive sputtering can be used to deposit one or more material in electrochromism lamination. Figure 11 is the figure for showing to become with oxygen concentration from the speed of sputtering target sputtering sedimentation under fixed power.As shown in Figure 11, In the presence of the relevant strong hysteresis effect of the oxygen concentration distribution for being exposed to target and/or having been operated wherein.For example, from hypoxemia When concentration starts and increases to higher oxygen concentration, sedimentation rate keeps at a relatively high, is formed not until oxygen concentration reaches sputtering target Untill the degree of the oxide that can be sufficiently rapidly removed from target.Now, sedimentation rate declines, and sputtering target is generally formed Metal oxide target.The sedimentation rate of oxide target is typically much lower than the sedimentation rate of metallic target, and every other condition is homogeneous Together.Sedimentation rate area relatively high in Figure 11 corresponds to metal deposit mode, and relatively low sedimentation rate area corresponds to gold Category oxide depositional mode.When target be then exposed to exposed to the operation of high oxygen concentration/under high oxygen concentration at the beginning it is relatively low During concentration/operate at relatively low concentration, sedimentation rate keeps at a fairly low, is jumped to higher until oxygen concentration reaches sedimentation rate Untill the degree of level.As shown in Figure 11, these change occur when oxygen concentration depending on oxygen concentration be increase or reduce without Together.By changing the magnetic strength of target power density and internal magnets 1003 the definite oxygen when mode changes generation can be controlled dense Degree.For example, if a target from surface sputter substantially more high-throughout metallic atom (be attributed to power higher and/ Or magnetic strength), then compared with the sputtering very target of the metallic atom of small throughput, the target will likely be maintained at metal deposit side Formula.This similar hysteresis effect can be used to promote deposition process.

Some embodiments of the material in electrochromism lamination are deposited using two or more sputtering targets wherein In, a target can be operated by metal depositional mode, and another target can be operated by metal oxide depositional mode.Controlled by with the time Target power density processed, the magnetic strength of internal magnets 1003 and each target be exposed to/atmosphere that operates wherein, can press simultaneously Two kinds in these modes operate.In an example, the first nickel tungsten target is made exposed to relatively low intensity of oxygen and then Bring it into the oxygen of intermediate concentrations so that it presses the operation of metal depositional mode.Make the second tin target exposed to the oxygen of rather high concentration And then bring it into the oxygen of intermediate concentrations so that it presses the operation of metal oxide depositional mode.Then can be by two target bands To together, intermediate oxygen concentration is still exposed to, wherein (the first target continues to press metal depositional mode in two ways using them Operation and the second target continue by metal oxide depositional mode operation) material is deposited to substrate.

In many cases, the different atmosphere exposure of each target may be not required.Except different history oxygen is sudden and violent Other factors outside dew may result in target and be operated by different depositional modes.For example, target may be attributed in target Different materials and there are different hysteresis curves.Thus, target enough may be operated differently, even if they are in history It is upper to be operated exposed to identical aerial oxygen condition and under the conditions of identical aerial oxygen.In addition, putting on the power of each target Amount can interfere significantly on the depositional mode that each target is experienced.Therefore, in an example, it is attributed to what is applied to each target Different capacity a, target presses the operation of metal depositional mode, and another target presses the operation of metal oxide depositional mode.This kind of method can Can be easier, because without target is separated from one another so that they can be exposed to different oxygen concentrations.Make target in hysteresis curve The advantage operated at difference is the composition that can nearly control institute's deposition materials.

Although it will be appreciated that the order that (and being implied in Fig. 2) deposition operation is illustrated in Fig. 5 is EC layers, the 2nd IC Layer and last CE layers, but the order can be overturned in various embodiments.In other words, when describing as described in this article When " order " of the layer of lamination is deposited, it is desirable to cover following " reverse " order：First CE layers, the 2nd IC layers and the 3rd EC layers, And above-described " forward direction " order.Forward sequence can play reliable high-quality electrochromism dress with reverse sequence both of which The effect put.Additionally it should be appreciated that being not limited to deposit this for depositing the condition of various EC, IC and CE materials as herein described Class material.In some cases, other materials can be deposited under the conditions of same or like.Additionally, in some cases, can save IC layers.In addition, can be formed using non-sputtered sedimentary condition being retouched with the situation of institute's sputter material in some embodiments The same or similar institute's deposition materials of material stated.

Because EC layers and each of the CE layers amount of the electric charge that can steadily keep changes, therefore the material depending on being used Depending on, the relative thickness of each of the layer can be in due course controlled to match capacity.In one embodiment, it is electroluminescent Photochromic layer includes that tungsten oxide and counterelectrode include nickel tungsten tin-oxide, and thickness and the counter electrode layer of electrochromic layer thickness The ratio of degree is about 1.7:1 and 2.3:Between 1 or about 1.9:1 and 2.1:(wherein about 2 between 1:1 is instantiation).

Referring again to Fig. 5, operation 720, after CE layers of deposition, EC laminations are completed.It is noted that in fig. 4, process operation 720 (referred to as " deposition laminations ") mean that EC laminations (are manufacturing the using tin indium oxide plus the second tco layer in this kind of situation During two TCO, sometimes referred to as " ITO ").In general, " lamination " refers in this manual EC-IC-CE layers；I.e. " EC is folded Layer ".Referring again to Fig. 5, in one embodiment, represented by process 728, tco layer is deposited on lamination.Referring to Fig. 2, this will Corresponding to the second tco layer 630 on EC laminations 625.Once process 728 is completed, technological process 720 terminates.It is generally but not certain, The sedimentary cover on EC laminations.In some embodiments, cap rock is SiAlO, similar with IC layers.For example,

Submitted to and entitled " FABRICATION OF LOW DEFECTIVITY on December 22nd, 2009 Further described for forming various layers in the U.S. Patent Application No. 12/645,111 of ELECTROCHROMIC DEVICES " The method and condition of (such as tco layer, electrochromic layer, counter electrode layer and electrode layer), what this application was quoted in full Mode is incorporated herein.

As mentioned, when EC laminations, wherein any during the making of lamination of substrate are made in depositing system is integrated Wait without departing from integration depositing system.In one embodiment, also using depositing system the second tco layer of formation is integrated, wherein serving as a contrast Bottom is during the deposition of EC laminations and tco layer without departing from integration depositing system.In one embodiment, depositing system is being integrated The middle all layers of deposition, wherein substrate are during depositing without departing from integration depositing system；In other words, in one embodiment, Substrate is glass plate, and make on the glass between being clipped in first and second tco layer including EC layers, IC layers and CE layers Lamination, wherein glass are during depositing without departing from integration depositing system.In another implementation of this embodiment, substrate is Glass, with the diffusion barrier deposited before entering in integration depositing system.In another implementation, substrate is glass, And diffusion barrier, it is clipped in being all deposited over including EC layers, IC layers and CE layers of lamination between first and second tco layer On glass, wherein glass during depositing without departing from integrate depositing system.

As mentioned above, when forming EC, CE and/or IC layer on substrate, lithium can along with them be provided.This may be related to And (such as) lithium is cooperatively sputtered with the other materials (such as tungsten and oxygen) to given layer.Some embodiments being described below In, deliver lithium via single process and allow to spread or be otherwise incorporated into EC, CE and/or IC layer.At some In embodiment, the only single layer in electrochromism lamination is lithiated.For example, in some instances, only anodic coloration CE Layer is lithiated.In other cases, only cathodic coloration EC layers is lithiated.In other cases, only IC layers is lithiated.

In some embodiments, electrochromism lamination includes the counter electrode layer with electrochromic layer direct physical contact, Between the two without ion conducting layer.Electrochromism and/or counter electrode layer may include oxygen-enriched with what other layers in these layers were contacted Part.Oxygen-rich fraction include oxygen concentration higher than the electrochromic material of the remainder of electrochromic layer and/or counter electrode layer or Counterelectrode material.The submission of on April 30th, 2010 is discussed further and is described according to such electrochromic device for designing and producing U.S. Patent number 8, in 300,298, the patent is incorporated herein by reference above.

In certain embodiments, the making of electrochromism lamination is carried out in depositing system is integrated.It is such to integrate system System can allow the various layers in lamination is deposited in the case of not destroying vacuum.In other cases, can be by needing from being protected The process removed in the vacuum environment of shield deposits one or more layers in lamination.For example, in some cases, use Physical vapour deposition (PVD) deposits one or more layers (such as cathodic coloration EC layers) on substrate under vacuo, then by substrate from true It is aerial to remove and carry out depositing ions conductor layer using sol-gel (or other are antivacuum) process, and then return substrate It is back to vacuum environment and counter electrode layer is coloured with deposition anode.Sol-gel process is related to produce solid material from small molecule.Will be single Body changes into colloidal solution, and the colloidal solution serves as the precursor of the integration networkses of discrete particles or network polymer.

The direct lithiumation of electrochromism lamination

In some embodiments, as mentioned above, the optics of electrochromic device lamination is responsible in the insertion of lithium ion The switching of state.It will be appreciated that lithium can be introduced into lamination by various means.For example, can be in the same of the material of sedimentary When lithium is provided one or more (such as while lithium deposition and tungsten oxides during forming EC layer) into these layers.However, In some cases, the process of Fig. 5 may be used to be delivered to lithium EC layers, IC layers and/or CE layers one or more behaviour Interrupt.For example, also lithium can be introduced via one or more single lithiation steps, wherein not depositing other substantially Element lithium is delivered in the case of material.Such lithiation step can occur after EC layers, IC layers and/or CE layers of deposition.Or (or in addition), one or more lithiation steps can be carried out between the step of being carried out for deposition single layer.For example, can lead to Cross and deposit first limited amount nickel tungsten tin-oxide, subsequent Direct precipitation lithium and then with deposit additional quantity nickel tungsten tin aoxidize Thing terminates to deposit counter electrode layer.Such method can have some advantages, such as preferably by lithium and ITO (or conductive layer its His material) isolation, which improve and adhere to and prevent undesired side reaction.Presented in Fig. 6 using the operation of single lithiumation Lamination forming process an example.In some cases, lithiumation behaviour is carried out in the deposition suspensory period to given layer Make, to allow to introduce lithium before the deposition of layer is completed.

Fig. 6 is illustrated for the technique stream with the similar mode of process 720 shown in Fig. 4 by stack deposition on substrate Journey 720a.As described by with regard to Fig. 5, technological process 720a include EC layer of deposition (operation 722), IC layers of deposition (operating 724) and CE layers of deposition (operation 726).However, due to increased lithiumation operation 723 and 727, technological process 720a is different from 720.One In individual embodiment, physical vapour deposition (PVD) is carried out to lithium using depositing system is integrated, wherein substrate is passed in electrochromic layer, ion During the sequential aggradation of conducting shell, counter electrode layer and lithium whenever without departing from integrate depositing system.

In certain embodiments, lithium deposition is carried out using high voltage lithium negative electrode, because in the absence of many during lithium is sputtered Secondary electrons are launched.In some embodiments, it is provided as realizing the power of sputtering and delivering via direct current (DC).At it In his embodiment, pulse DC/AC reactive sputterings are used.An embodiment of pulse DC/AC reactive sputterings is used wherein In, frequency between about 20kHz and about 400kHz, in another embodiment between about 100kHz and about 300kHz, again In one embodiment between about 200kHz and about 250kHz, for about 220kHz in another embodiment.Use lithium target.One In individual embodiment, the target in about 80% (by weight) and 100%Li between, in another embodiment about 90% with Between about 99%Li, for about 99%Li in another embodiment.Generally, the extreme reactivity of element lithium is attributed to, in inertia Lithiumation is carried out in environment (such as single argon).For the power density that is sputtered to lithium target in about 1 watt/cm²With about 10 Watt/cm²Between (based on substrate deposition table area and determine)；In another embodiment in about 2 watts/cm²With about 4 watts Spy/cm²Between；In yet another embodiment in about 2.5 watts/cm²With about 3 watts/cm²Between；It is in another embodiment About 2.7 watts/cm².In one embodiment, lithium sputtering is carried out under the pressure between about 1 millitorr and about 20 millitorrs, another In one embodiment between about 5 millitorrs and about 15 millitorrs, for about 10 millitorrs in another embodiment.Can by conditions above that This in any combination, to realize the deposition of high-quality lithiumation process.

In one embodiment, as be deposited on lithium on EC layers and CE layers by double lithiumation process 720a displayings.As above After literary described EC layers of deposition (operation 722), lithium is sputtered on EC layers；Referring to operation 723.Hereafter, IC layers of (operation is deposited 724), subsequent CE layers (operation 726).Then, lithium is deposited on CE layers；Referring to operation 727.(for example) EC layers is oxygen wherein Change tungsten and for an embodiment of the about twice thickness of CE layer of nickel tungsten tin-oxide in, added to lamination lithium total amount in EC Layer and CE layers between into ratio be for about 1:3 to 2:3 ratio；In other words, EC is sputtered with added to the 1/3 of total lithium of lamination Layer, and CE layers is then with about the 2/3 of total lithium.In a specific embodiment, added to lamination lithium at EC layers with CE layers Between into ratio be for about 1:2 ratio.

It is as explained above in an embodiment of double lithiations, EC layers is processed with enough lithiums with Meet the requirement that EC materials irreversibly fetter lithium (with (such as) compensation " blind electric charge ").Lithium needed for Reversible Cycle is added to CE layers (it is also possible to have blind electric charge).In certain embodiments, can be by the optical density (OD) of EC layers of the monitoring when lithium is added To be titrated to the lithium needed for compensating blind electric charge, because will with EC layers before blind electric charge is fully compensated enough lithiums have been added Color will not generally be changed.

In some cases, lithiumation process is carried out in position using isolation scheme.In an example, using whole The isolating valve closed in depositing system carries out carrying out isolation scheme.For example, after substrate is moved in lithiumation station, isolating valve is shut Think prepared by lithiumation to separate and for example be rinsed with argon or evacuated substrate with other stations.In another embodiment, lead to Cross and manipulate controlled surrounding environment, such as by the differential pressure in the lithiumation station via integration depositing system in controlled surrounding environment It is middle to form flowing dynamic so that lithium deposits and is sufficiently separated to realize isolating with other processes integrated in depositing system.Another In one embodiment, the combination of above-mentioned condition is used.For example, valve can be closed partly (or can configure to lithiumation station, make Substrate inlet hole and/or outlet opening are minimized), and using one or more hydrodynamics come by lithiumation process with it is adjacent Process further keep apart.Referring again to Fig. 6, after the double lithiumation processes as described in operation 722 to 727, as above Literary described deposition (second) tco layer (operation 728).

Fig. 7 is illustrated for by another technological process 720b in stack deposition to substrate.The technique of the process and Fig. 4 Flow 700 is similar to.As described by with regard to Fig. 5, technological process 720b includes EC layers of deposition (operation 722), IC layers of deposition (operation 724) And CE layers of deposition (operation 726).However, technological process 720b is different from 720, because in the presence of the lithiumation operation 727 of insertion. In this embodiment of the process of stack deposition, lithium is delivered to by during lamination makes and/or after lamination makes CE layers and allow lithium via diffusion be embedded in EC layers through IC layers in add lithium in need.

Multistep heat chemistry is adjusted

Referring again to Fig. 4, once deposited lamination, multistep heat chemistry regulation (MTC) process is carried out to device (referring to square frame 730).Generally, MTC processes are only carried out after all layers for having formed electrochromism lamination.It is noted that MTC processes can be Complete ex situ is carried out, i.e. in the outside of the integration depositing system for depositing lamination, or at least partially or fully original position is entered OK, i.e. moved on to for making lamination without (such as) destruction vacuum or otherwise by substrate inside depositing system Outside controlled surrounding environment.In certain embodiments, the initial part of MTC processes is that original position is carried out, and it of the process It is partly afterwards that non-original position is carried out.In certain embodiments, before the deposition of some layers, such as in the deposition of the second tco layer The part of MTC is carried out before.

According to some embodiments, hot place (for example under an inert gas) is carried out to device first under the conditions of non-reacted Reason.In a specific embodiment, device is heated about 5 minutes to about 30 at a temperature of between about 200 DEG C with about 350 DEG C Minute.In certain embodiments, this operation is carried out at reduced pressure or vacuum.Next, to device under reactive conditions It is heat-treated.In some embodiments, this be related to by device oxidizing atmosphere (such as oxygen and inert gas, about 10 to 50 millitorrs) middle annealing.In a particular embodiment, annealed under the pressure higher than non-reacted heat treatment step.One In individual specific embodiment, device is heated about 3 minutes to about 20 minutes at a temperature of between about 200 DEG C with about 350 DEG C.

Optionally, after oxidizing annealing, the heating in air (dystopy) by device.In one embodiment, will fill Put and heated about 1 minute to about 60 minutes at about 150 DEG C to about 500 DEG C, in another embodiment at about 200 DEG C to about 400 Heated at DEG C about 5 minutes to about 30 minutes.It will be appreciated that MTC processes may include that two, three or more is independent and different Operation.Three operations described here are provided merely for the sake of the purpose for illustrating methods described.In addition, the work presented at this Skill condition is suitable for building glass, but recognizes that the time of heater depends on the size of device, for other application May have to be scaled.After the completion of MTC processes, device is to be processed further getting ready.

As mentioned above, it may be necessary to which additional layer (is returned with realizing the optical property (such as antireflection) for improving, durability Because being disposed in physics), sealing etc..The addition of one or more in these layers is intended to be included in embodiment party as described above In Additional embodiments outside case.

Lithiumation described herein and high-temperature process operation can influence various materials in electrochromism lamination composition and Structure.As an example, include with anodic coloration CE layers cathodic coloration EC layers of directly contact (therebetween in electrochromism lamination Do not deposit single ion conducting layer) in the case of, change negative electrode between, the layers at the interface area that heat treatment operation can be and Color EC layers and anodic coloration CE layers of composition and/or structure, is consequently formed the region with ionic conduction, electrical insulation characteristics.Class As, lithiumation and heat treatment operation may influence the Nomenclature Composition and Structure of Complexes of anodic coloration counter electrode layer.In all cases, pass through This generic operation improves anodic coloration counter electrode layer.

For the manufacturing process of finishing device

Referring again to Fig. 4, second laser delineation (square frame 740) is carried out.In substrate perpendicular to the two of first laser delineation Side carries out laser grooving and scribing 740 near the outward flange of lamination across the length of substrate.Fig. 3 is shown by the shape of laser grooving and scribing 740 Into groove 626 position.This delineation is also performed until substrate to enter one from a TCO (and diffusion barrier, if in the presence of) The isolated part (the first busbar will be connected wherein) and the laminated coating of the isolation edge of step the first tco layer of isolation (such as near shade) is minimizing the short circuit that causes because deposition rolls out that stack layer is outer.

Next, the relative with first laser delineation of substrate and parallel to first laser delineation adjacent edges along The circumference of lamination carries out the 3rd laser grooving and scribing 745.This 3rd laser grooving and scribing is only arrived and is enough to isolate the second tco layer and EC laminations deeply, And do not cut through the first tco layer.Referring to Fig. 2, laser grooving and scribing 745 forms groove 635, and the groove is by EC laminations and the 2nd TCO Homogeneous conformal part isolates with outermost edge part, and the outermost edge part may meet with and roll out (such as such as institute's exhibition in Fig. 2 Show, by cutting 625 and 630 part near region 650 of floor that groove 635 is isolated) and therefore in area 650 first Short circuit is caused between the second tco layer, wherein the second busbar will be attached near area 650.Groove 635 is also by the 2nd TCO's Area is rolled out to isolate with the second busbar.Groove 635 is also show in Fig. 3.

Referring again to the process 700 in Fig. 4, after the 3rd laser grooving and scribing, busbar (process 750) is attached.In connection After busbar, device is integrated into (process 755) in IGU.Pad or seal are placed (for example by the circumference around substrate It is made up of PVB (polyvinyl butyral), PIB or other suitable elastomers) form IGU.It is generally but not certain, during assembly Drier is included in IGU frameworks or spacer bar to absorb any moisture.In one embodiment, seal is impaled and confluxed Bar and reach the electrical lead of busbar and extend through seal.At seal after appropriate position, by second glass Glass is placed on seal, and is filled with inert gas (usually argon) by the generation of substrate, the second sheet glass and seal Volume.Once IGU is completed, process 700 is completed.The IGU that can be completed is arranged on (for example) in glass plate, framework or curtain wall simultaneously And electric power source and controller are connected to operate electrochromic.

In addition to regard to the process steps described by above method, also edge removal step can be added to the technique stream Journey.Edge is removed by a part for the manufacturing process in electrochromic device to be integrated into (such as) window, wherein in dress Put removal before in being integrated into window and roll out thing (as described by with regard to Fig. 2).In the case of using without preventing glass, should extend The removal of the coating (for long-term reliability and unwanted) below to IGU frameworks is the reach in IGU is integrated into Remove.Intend to include this edge removal process in above method, as the alternate embodiment of embodiment listed above.

In certain embodiments, different technological processes are can be used to make electrochromic device.In June 4 in 2014 Day submission and the U.S. Patent Application No. 14/362,863 of entitled " THIN-FILM DEVICES AND FABRICATION " In further discuss the technological process of replacement, the application is incorporated herein in entirety by reference.For example, if Use such technique, then EC devices can be delineated without isolation.

Integrate depositing system

It is as explained above, electrochromic device can be made on (such as) building glass using depositing system is integrated. As described above, IGU is manufactured using electrochromic device, the IGU is used to manufacture electrochromic again.Term " is integrated Depositing system " means the equipment for making electrochromic device on optical clear and translucent substrate.The equipment tool There are multiple stations, it is each responsible for discrete cell operation, such as deposits the specific components (or part of component) of electrochromic device, And the cleaning of such device or part thereof, etching and temperature control.Fully integrated at the multiple station so that made above The substrate for making electrochromic device can be sent to next station without being externally exposed environment from a station.Integration herein Depositing system is worked in the case where internal system has controlled surrounding environment, wherein the treating stations are located at the environment In.The system fully integrated realizes the more preferable control to the interface quality between the layer that is deposited.Interface quality refer to except Pollutant lacks in the quality of the adhesion outside other factors between all floor and interface area.Term " controlled surrounding environment " Mean the sealed environment for external environment condition (such as open atmospheric environment or clean room) separate.In controlled surrounding environment, Come at least one of control pressure and gas composition independently of the condition in external environment condition.In general but not necessarily, it is controlled Surrounding environment there is the pressure of subatmospheric power；For example, at least partial vacuum.Condition in controlled surrounding environment can be Keep constant or can time to time change during treatment operation.For example, can be in controlled surrounding environment under vacuo The layer of electrochromic device is deposited, and at the end of deposition operation, the environment can be backfilled with purge gas or reagent gas, And pressure increases to (such as) atmospheric pressure to be processed at another station, and then re-establishes vacuum to enter Next operation of row etc..

In one embodiment, the system includes multiple deposition stations, and the multiple deposition station continuously aligns and mutually Even and operable it is sent to next station without exposing the substrate to external environment condition from station with by substrate.It is the multiple Deposition station includes first deposition station of (i) containing one or more targets for depositing cathodic coloration electrochromic layer；(ii) contain There is the second deposition station of one or more targets for depositing ions conducting shell；And (iii) is containing for depositing counter electrode layer One or more targets the 3rd deposition station.In some cases, the second deposition station can be saved.For example, the equipment can Do not include any target for depositing single electrode layer.

The system also includes controller, and the controller contains for be sequentially deposited (i) electroluminescent change on substrate Chromatograph, (ii) (optional) ion conducting layer and (iii) counter electrode layer to form lamination in the way of substrate is transported through into institute State the programmed instruction at multiple stations.In one embodiment, the multiple deposition station is operable transmits with by substrate from a station To next station without destruction vacuum.In another embodiment, the multiple deposition station is configured to be served as a contrast in building glass Electrochromic layer, optional ion conducting layer and counter electrode layer are deposited on bottom.In another embodiment, depositing system is integrated Including it is operable with the multiple deposition station when by building glass substrate with the substrate holder of vertically-oriented fixing And conveying mechanism.In yet another embodiment, integrating depositing system includes being used between external environment condition and integration depositing system Transmit one or more load locks of substrate.In another embodiment, the multiple deposition station is included for depositing Selected from least the two of the layer of the group being made up of cathodic coloration electrochromic layer, ion conducting layer and anodic coloration counter electrode layer Individual station.

In some embodiments, integrating depositing system includes one or more lithium deposition stations, one or more of lithiums Deposition station each includes the target containing lithium.In one embodiment, integrate depositing system and contain two or more lithium deposition stations. In one embodiment, integrate depositing system have for single treating stations are isolated from each other during operation one or Multiple isolating valves.In one embodiment, one or more of lithium deposition stations have isolating valve.In this document, term " isolating valve " means to be used in depositing system is integrated by the deposition carried out at a station or other treatment and at other stations Treatment isolation device.In an example, isolating valve be integrate depositing system intrinsic deposition lithium when engage physics (Gu Body) isolating valve.Actual physical solid valve is engageable to lithium deposition with other treatment or station integrated in depositing system completely Or it is partially isolating (or shielding).In another embodiment, isolating valve can be gas knife or shielding, for example make argon gas or other The partial pressure of inert gas passes over to prevent ion flow to other stations from the region between lithium deposition station and other stations.Another In one example, isolating valve can be depression between lithium deposition station and other treating stations so that enter depression lithium ion or Ion from other stations is moved to (such as) waste liquor stream rather than the neighbouring treatment of pollution.This is deposited via integration Differential pressure in the lithiumation station of system is dynamically realized via the flowing in controlled surrounding environment so that lithium deposited and deposit with integrating Other treatment in system are sufficiently separated.Again, isolating valve is not limited to lithium deposition station.

Fig. 8 A schematically illustrate the integration depositing system 800 according to some embodiments.In this example, system 800 include sample introduction load locks 802, for substrate to be introduced in system；And go out sample load locks 804, use Removed from system in by substrate.The load locks allow substrate to be introduced into and removal system receiving without perturbed system The surrounding environment of control.Integrating depositing system 800 has module 806, and the module has multiple deposition stations；EC layers of deposition station, IC Layer deposition station and CE layers of deposition station.In the broadest sense, integration depositing system need not have herein loads locking Device, such as module 806 can be used as alone to integrate depositing system.For example, substrate can be insmoded in 806, foundation is received The surrounding environment of control and then by the various stations in system substrate is processed.Integrate the single station in depositing system Having heaters, cooler, various sputtering targets can be contained and be used to move their component, RF and/or D/C power and electric power is passed Send mechanism, etch tool (such as plasma etching), gas source, vacuum source, glow discharge source, procedure parameter monitor and biography Sensor, robot, power supply etc..

Fig. 8 B are with perspective view and the section (or simplification view) for integrating depositing system 800 is shown in more detail, including Internal cut-away view.In this example, system 800 is modular, wherein by sample introduction load locks 802 and going out sample dress Carry locking device 804 and be connected to deposition module 806.In the presence of (the dress of import 810 for being loaded into (such as) building glass substrate 825 Carrying locking device 804 has corresponding outlet).Substrate 825 is supported by supporting plate 820, and the supporting plate is advanced along track 815. In this example, supporting plate 820 is supported via suspension by track 815, but supporting plate 820 can be also supported on positioned at the bottom of equipment 800 Track or (such as) near portion are located on the top of the track in the middle of the top and bottom of equipment 800.Carried on June 9th, 2014 Friendship and the P.C.T. number of patent applications PCT/US14/ of entitled " GLASS PALLET FOR SPUTTERING SYSTEMS " 41569 further in describe for making electrochromic device supporting plate, the patent application is incorporated in entirety by reference Herein.Supporting plate 820 can forwardly and/or backwardly translate (as indicated by double-head arrow) by system 800.For example, in lithium During deposition, substrate can be made forwardly and rearwardly to be moved before lithium target 830, caused repeatedly by realize desired lithiumation. Supporting plate 820 and substrate 825 take substantially vertical orientation.Substantially vertical being orientated is nonrestrictive, but it can help prevent Only defect, because gravity (for example) may will be tended to submit to simultaneously by the particle matter of the agglomerating generation of the atom from sputtering And therefore will not be deposited on substrate 825.Additionally, because building glass substrate tends to larger, substrate is crossing integration The vertically-oriented during station of depositing system makes it possible to the relatively thin glass substrate of coating, because the problem of sagging aspect is less, and This can occur in thicker hot glass.

Target 830 (being in this case cylindrical target) is oriented substantially parallel to substrate surface and in substrate table Before face, deposition will occur (for convenience, do not show other sputtering components herein) at substrate surface.Substrate 825 exists It is translatable during deposition to be moved before substrate 825 by target 830, and/or target 830.The mobile route of target 830 is not limited to edge The path shift of substrate 825.Target 830 can along through its length axle rotation, along substrate path (forward and/or to Translate afterwards), moved by circular path along perpendicular to the path shift in the path of substrate, in parallel to the plane of substrate 825 Deng.Target 830 need not be cylinder, it can be plane or be deposition have desired characteristics want layer needed for any shape Shape.Additionally, there may be in each deposition station more than a target, and/or target is visually wanted process and is moved between stations.

Integrating depositing system 800 also has the various vavuum pumps set up in system and maintain controlled surrounding environment, enters Gas port, pressure sensor etc..These components have been not shown, but will be understood by persons skilled in the art.For example via Computer system or other controllers (in the fig. 8b by LCD and keyboard representation) 835 carry out control system 800.The general skill in this area Art personnel will be appreciated that embodiment herein can be used and be related to be stored in one or more computer systems or via one Or the various processes of the data of multiple computer system transmission.Embodiment of the present invention is further related to for performing these operations Equipment, such computer and microcontroller.Can be using these equipment and process come deposition process and quilt described herein It is designed for realizing the electrochromic material of the equipment of these methods.Control device can be specifically constructed to for required mesh , or it can be all-purpose computer, the all-purpose computer is by the computer program and/or data knot that are stored in computer Structure optionally starts or reconfigures.Process presented herein has no intrinsic phase with any certain computer or other equipment Guan Xing.Especially, various general-purpose machinerys can be used together with the program write according to teachings herein, or is constructed more special The equipment of doorization may be more convenient come the method and process needed for carrying out and/or controlling.

As mentioned, the various stations for integrating depositing system can be modular, but once connect, and form continuous system, Controlled surrounding environment is wherein set up and maintained to process substrate at the various stations in system.Fig. 8 C illustrate integration deposition System 800a, its similar to system 800, but in this example, each station be it is modular, specifically, be EC stops 806a, IC stop 806b and CE stops 806c.In a similar embodiment, IC stops 806b is removed.Modular form is not It is required, but it is for convenience because depending on the needs, can be needed according to customization and emerging technique progress come assemble integrate it is heavy Product system.For example, Fig. 8 D are illustrated with two integration depositing system 800b of lithium deposition station 807a and 807b.System 800b (such as) is equipped to method implemented as described above, such as combines double lithiations of Fig. 6 descriptions.It is also possible to use System 800b comes (for example) described in conjunction with Figure 7 by implementing during the treatment of substrate (such as) merely with lithium station 807b Single lithiation.But in the case of modular form, if for example single lithiumation is to be wanted process, then one in lithiumation station For unnecessary, and can be used such as the system 800c shown in Fig. 8 E.System 800c only has a lithium deposition station 807.

System 800b and 800c also have the tco layer station 808 for depositing tco layer on EC laminations.Depending on process requirements It is fixed, extra station can be added to depositing system is integrated, such as cleaning the station of process, laser grooving and scribing, cap rock, MTC etc..

Experimental result

Test result indicate that disclosed NiWSnO materials show very high-quality coloring properties.Especially, NiWSnO materials under its non-colored state very clear (transparent), with the other materials phase somewhat coloured under non-colored state Than with less color (particularly yellow).

NiWSnO is deposited

By substrate in the deposition chamber it is front and rear scan when, using repeated deposition it is very thin sputter material layer it is mixed to deposit The nickel tungsten tin-oxide NiWSnO of conjunction.Using under the chamber pressure of about 10 millitorrs, NiW is closed in the mixture of argon and molecular oxygen The reactive sputtering of gold and Sn metallic targets.NiW alloys targets are produced using high temperature insostatic pressing (HIP) (HIP) method.It is synchronized using two Pulsed DC source supply independently controls the power supply to each target.Sn is adjusted by changing the power ratio between two targets With the ratio of Ni+W.Can be changed by increaseing or decreasing speed of the substrate when deposition chambers are moved through in one group of given work( The thickness of the NiWSnO under the conditions of rate.In order to realize the thickness of wanting of whole counterelectrode, increase or decrease before target on demand The pass of process.By adjusting Ar and O in sputter gas₂Partial pressure and gross pressure control the degree of oxidation of film.By behaviour These procedure parameters are indulged, ratio NiW is can control:Sn:O.Realize temperature change using heater, but peak performance film and dress Put typically to be deposited in the case of without extra heating and form.Underlayer temperature is usually less than 100 DEG C.

As example, it is arranged on by using the power and substrate speed that are selected to realize every thickness all over less than 5nm Sputtered to realize high performance counterelectrode in pure oxygen environment.Film thickness is built more than 150 times by depositing system.Selection For two power supply units of sputtering target so that NiW power (e.g., from about 6kW) is about 12 times of Sn power (0.5kW).Use RBS measures gained Ni:(W+Sn) ratio for about 2.The performance using the device of this counterelectrode preparation is listed below.

The embodiment of the performance improvement caused by NiWSnO materials

Following table compares the device with NiWSnO anodic coloration counterelectrodes and has NiWO anodic coloration counter electrode layers The all solid state key metrics compared with inorganic electrochromic device.Except the material of counterelectrode is different, device is in other respects All same.In this embodiment, described device both of which uses tungsten oxide cathodic coloration electrochromic layer.It is anti-electric with NiWSnO The photopic vision transmittance (photopic transmission) of the device of pole has small increase and quantitative device in transmission The CIE coordinates (b*) of yellow appearance are substantially reduced.In other words, the significantly lower b* of the device with NiWSnO counterelectrodes shows There is less yellow under property/clear state wherein in this device.Because counterelectrode needs to serve as electric charge storage layer, following table show with Device is colored as the improvement that cost does not obtain transmittance in a neutral state, and this is filled relative to the comparing with NiWO counterelectrodes Putting slightly improves.

Although having described foregoing embodiments in more detail to facilitate understanding, described embodiment should be regarded For illustrative and not restrictive.Persons skilled in the art will be evident that, can in the category of appended claims Some are put into practice to change and change.

Claims

1. a kind of method for making electrochromism lamination, methods described includes：

Cathodic coloration layer is formed, the cathodic coloration layer includes cathodic coloration electrochromic material；And

Anodic coloration layer is formed, the anodic coloration layer includes nickel-tungsten-tin-oxide (NiWSnO).

2. the method for claim 1, wherein the NiWSnO includes about 1:1 and 4:Ni between 1:(W+Sn) atom Than.

3. method as claimed in claim 2, wherein the NiWSnO includes about 1:1 and 3:Ni between 1:(W+Sn) atom Than.

4. method as claimed in claim 3, wherein the NiWSnO includes about 2:1 and 3:Ni between 1:(W+Sn) atom Than.

5. method as claimed in claim 3, wherein the NiWSnO includes about 1.5:1 and 2.5:Ni between 1:(W+Sn) it is former Son ratio.

6. method as claimed in claim 5, wherein the NiWSnO includes about 2:1 and 2.5:Ni between 1:(W+Sn) atom Than.

7. the method as any one of claim 1 to 6, wherein the NiWSnO includes about 1:9 and 9:W between 1:Sn Atomic ratio.

8. method as claimed in claim 7, wherein the NiWSnO includes about 1:1 and 3:W between 1:Sn atomic ratios.

9. method as claimed in claim 8, wherein the NiWSnO includes about 1.5:1 and 2.5:W between 1:Sn atomic ratios.

10. method as claimed in claim 9, wherein the NiWSnO includes about 1.5:1 and 2:W between 1:Sn atomic ratios.

11. method as any one of claim 1 to 10, wherein form the anodic coloration layer including to one or many Individual sputtering target is sputtered to form the NiWSnO.

12. methods as claimed in claim 11, wherein at least one of the one or more of bags in the sputtering target Containing the metal element selected from the group for consisting of：Nickel, tungsten and tin.

13. method as described in claim 11 or 12, wherein in one or more of in the sputtering target at least one It is individual comprising alloy, the alloy is selected from the metal of the group for consisting of comprising two or more：Nickel, tungsten and tin.

14. method as any one of claim 11 to 13, wherein in one or more of in the sputtering target At least one include oxide.

15. method as any one of claim 1 to 14, wherein anodic coloration layer is substantially unbodied.

16. method as any one of claim 1 to 15, wherein being in direct physical contact with each other and forming the negative electrode and Chromatograph and anodic coloration layer, do not deposit single electrode layer between them.

17. method as any one of claim 1 to 16, wherein cathodic coloration layer includes tungsten oxide, optionally mixes It is miscellaneous by one or more selected from the dopant of group being made up of molybdenum, vanadium and titanium.

A kind of 18. electrochromism laminations, it includes：

Cathodic coloration layer, the cathodic coloration layer includes cathodic coloration material；And

Anodic coloration layer, the anodic coloration layer includes nickel-tungsten-tin-oxide (NiWSnO).

19. electrochromism laminations as claimed in claim 18, wherein the NiWSnO includes about 1:1 and 4:Ni between 1:(W + Sn) atomic ratio.

20. electrochromism laminations as claimed in claim 19, wherein the NiWSnO includes about 1:1 and 3:Ni between 1:(W + Sn) atomic ratio.

21. electrochromism laminations as claimed in claim 20, wherein the NiWSnO includes about 2:1 and 3:Ni between 1:(W + Sn) atomic ratio.

22. electrochromism laminations as claimed in claim 20, wherein the NiWSnO includes about 1.5:1 and 2.5:Between 1 Ni:(W+Sn) atomic ratio.

23. electrochromism laminations as claimed in claim 22, wherein the NiWSnO includes about 2:1 and 2.5:Ni between 1: (W+Sn) atomic ratio.

The 24. electrochromism lamination as any one of claim 18 to 23, wherein the NiWSnO includes about 1:9 and 9: W between 1:Sn atomic ratios.

25. electrochromism laminations as claimed in claim 24, wherein the NiWSnO includes about 1:1 and 3:W between 1:Sn Atomic ratio.

26. electrochromism laminations as claimed in claim 25, wherein the NiWSnO includes about 1.5:1 and 2.5:Between 1 W:Sn atomic ratios.

27. electrochromism laminations as claimed in claim 26, wherein the NiWSnO includes about 1.5:1 and 2:W between 1: Sn atomic ratios.

The 28. electrochromism lamination as any one of claim 18 to 27, wherein anodic coloration layer is for substantially It is unbodied.

The 29. electrochromism lamination as any one of claim 18 to 28, wherein anodic coloration layer includes first The [amorphous of material, it has the farmland of the second material being dispersed in the whole [amorphous.

The 30. electrochromism lamination as any one of claim 18 to 29, wherein cathodic coloration layer and the sun Pole dyed layer direct physical contact.

The 31. electrochromism lamination as any one of claim 18 to 30, wherein cathodic coloration layer includes oxidation Tungsten, is optionally doped with one or more dopant selected from the group being made up of molybdenum, vanadium and titanium.

A kind of 32. integration depositing systems for making electrochromism lamination, the system includes：

Multiple deposition stations, the multiple deposition station continuously aligns and interconnects and operable be sent to from a station with by substrate Next station, without making the substrate be externally exposed environment, wherein the multiple deposition station includes

I () first deposition station, first deposition station contains one or more material sources for depositing cathodic coloration layer；

(ii) the second deposition station, second deposition station contains for depositing the sun comprising nickel-tungsten-tin-oxide (NiWSnO) One or more material sources of pole dyed layer；And

Controller, the controller is included to be used to deposit (i) described cathodic coloration layer and (ii) described sun over the substrate Pole dyed layer to form lamination in the way of the substrate is transported through the programmed instruction at the multiple station, the lamination is included extremely Few cathodic coloration layer and anodic coloration layer.

33. integration depositing systems as claimed in claim 32, wherein the NiWSnO includes about 1:1 and 4:Ni between 1:(W + Sn) atomic ratio.

34. integration depositing systems as claimed in claim 33, wherein the NiWSnO includes about 1:1 and 3:Ni between 1:(W + Sn) atomic ratio.

35. integration depositing systems as claimed in claim 34, wherein the NiWSnO includes about 2:1 and 3:Ni between 1:(W + Sn) atomic ratio.

36. integration depositing systems as claimed in claim 34, wherein the NiWSnO includes about 1.5:1 and 2.5:Between 1 Ni:(W+Sn) atomic ratio.

37. integration depositing systems as claimed in claim 36, wherein the NiWSnO includes about 2:1 and 2.5:Ni between 1: (W+Sn) atomic ratio.

The 38. integration depositing system as any one of claim 32 to 37, wherein the NiWSnO includes about 1:9 and 9: W between 1:Sn atomic ratios.

39. integration depositing systems as claimed in claim 38, wherein the NiWSnO includes about 1:1 and 3:W between 1:Sn Atomic ratio.

40. integration depositing systems as claimed in claim 39, wherein the NiWSnO includes about 1.5:1 and 2.5:Between 1 W:Sn atomic ratios.

The 41. integration depositing system as described in claim 340, wherein the NiWSnO includes about 1.5:1 and 2:W between 1: Sn atomic ratios.

The 42. integration depositing system as any one of claim 32 to 41, wherein for depositing the anodic coloration layer At least one of one or more of material sources comprising the metal element selected from the group for consisting of：Nickel, tungsten with And tin.

The 43. integration depositing system as any one of claim 32 to 42, wherein for depositing the anodic coloration layer At least one of one or more of material sources include alloy, the alloy is selected from by following comprising two or more The metal of the group of composition：Nickel, tungsten and tin.

The 44. integration depositing system as any one of claim 32 to 43, wherein for depositing the anodic coloration layer At least one of one or more of material sources include oxide.

The 45. integration depositing system as any one of claim 32 to 44, wherein by the depositing system be configured to by The anodic coloration layer is deposited as substantially unbodied material.

The 46. integration depositing system as any one of claim 232 to 45, wherein the integration depositing system is configured Into depositing cathodic coloration layer and anodic coloration layer with being in direct physical contact with each other.

The 47. integration depositing system as any one of claim 32 to 46, wherein for depositing the anodic coloration layer At least one of one or more of material sources be the sputtering target comprising nickel, tungsten and tin.

The 48. integration depositing system as any one of claim 32 to 47, it further includes one or more lithium sources.

49. integration depositing systems as claimed in claim 48, wherein the controller is comprising for in the cathodic coloration The substrate is transported through the mode of lithium deposition the instruction at the multiple station on layer and/or on anodic coloration layer.

50. integration depositing systems as claimed in claim 49, wherein the controller is comprising for in the cathodic coloration The substrate is transported through the instruction at the multiple station on layer with the mode of the upper lithium deposition of anodic coloration layer.